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The goal of this investigation was to optimize the synthesis of silazane-based polymers for processing fibre-reinforced ceramic matrix composites (CMCs). Liquid oligomeric silazanes were synthesized by ammonolysis of chlorosilanes and characterized spectroscopically (FTIR, NMR) as well as by elemental analysis. The silazanes were obtained in high yield and purity. Different functional groups (system S1: Si-H, Si-CH 3 , Si-CH = CH 2 ) and different degrees of branching in the Si-N backbone [system S2; Si(NH) 3 , Si(NH) 2 ] were realized in order to study the properties of the silazanes that are dependent on the molecular structure.For processing ceramics via pyrolysis of pre-ceramic oligomers, molecular weight, rheological behaviour, thermosetting and ceramic yield were investigated systematically and correlated with the molecular structure of the silazanes. Low molecular weights (500-1000 g mol Ϫ 1 ) as well as low viscosity values (0.1-20 Pa s) enable processing of the silazanes in the liquid phase without any solvent. Due to the latent reactivity of the functional groups, curing of the polymers via hydrosilylation is achieved.Structural changes and weight loss during polymer curing as well as the organic/inorganic transition were monitored by FTIR spectroscopy and differential thermogravimetric analysis. With increasing temperature (room temperature to 800°C) the hydrogen content decreases from 7 to < 0.5 wt% due to the formation of gaseous molecules (NH 3 , CH 4 , H 2 ). High ceramic yields up to 80% were reached by branching the oligomers, thus reducing the amount of volatile precursor fragments.Up to 1300°C, ceramic materials remained amorphous to X-rays. At higher temperatures (1400-1800°C) either SiC or SiC/Si 3 N 4 composites were selectively crystallized, depending on the pyrolysis conditions. The utility of the optimized precursors for CMCs has been demonstrated by infiltration of fibre preforms and subsequent pyrolysis.

Monolithic mullite with low sintering shrinkage was synthesized from polymer/filler blends-that is, siloxane/ alumina (siloxane/Al 2 O 3 ) (and siloxane/aluminum (siloxane/Al)) mixtures. The synthesis was based on a reactionbonding process of amorphous silica, which formed when the siloxane was oxidized, with Al 2 O 3 (or oxidized aluminum filler) at temperatures >1250°C. Thermodynamic calculations were used to calculate the phase composition at equilibrium. Thermoanalytical, infrared-spectroscopic, and microscopic techniques were applied to reveal the microstructural evolution. The corresponding volume changes were used to evaluate the linear shrinkage, based on the quantitative phase assemblage.

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