Thomas Ebert

Hybrid materials consisting of three different components were synthesized by the polymerization of one heterotrifunctional monomer in just one reaction step using, at the most, one catalyst. The polymerization of 2-furfuyloxy-2-methyl-4H-1,3,2-benzodioxasiline leading to a hybrid material consisting of phenolic resin, poly(furfuryl alcohol), and polymethylsilsesquioxane is, to the best of our knowledge, the first polymerization of this kind. The influence of different catalysts on the polymerization behavior and thus on the structure of the hybrid material was investigated. In accordance with the term “twin polymerization”, which is used for the polymerization of one monomer yielding two separate polymers, this type of polymerization could be called “triple polymerization”. The term “multiple polymerization” is introduced as a general term for the underlying concept of the synthesis of multiple polymers starting from one monomer in one process step.

Uncoated SiC fibres in SiC/SiC composites manufactured by the liquid-silicon infiltration (LSI) process show a strong degradation as a result of silicon attack. The goal of this research is the development of a SiN_x-based fibre coating, which acts as a barrier against the liquid silicon. The coating is applied by means of low-pressure chemical vapour deposition (LPCVD) utilising the gaseous precursors silane (SiH₄) and ammonia (NH₃) on a commercial SiC multifilament yarn. The result is an amorphous fibre coating with an increasing coating thickness and a variable chemical composition from the middle of the yarn to the edges. The coated fibres exhibit a reduced characteristic Weibull strength in comparison to the uncoated fibres. In order to examine the stability of the films, the coated fibres undergo a heat treatment at 1450 °C in different environments (vacuum, argon and nitrogen). In all environments, the amorphous SiN_xcoatings crystallise to the trigonal Si₃N₄. Depending on the coating thickness cracks and defects develop. However, the best results and the lowest amount of damaging occurs during the treatment in nitrogen.

SiC/SiC ceramics consist of silicon carbide fibres embedded in a silicon carbide matrix. As an alternative to classic CVI and PIP routes, Liquid Silicon Infiltration (LSI) was chosen as a technique with short process times to obtain composites with low porosity. Silicon carbide composites show good thermal shock resistance, a low coefficient of thermal expansion and excellent physical and chemical stability at elevated temperatures and are therefore regarded as promising candidates for various applications in jet engines and in power engineering. To build up the matrix, different phenolic resin based carbon precursors were infiltrated in fibre preforms and thermally cured, pyrolysed and siliconized. The aim is to obtain a high carbon yield during pyrolysis and to control the pore morphology in a way that the following liquid silicon infiltration leads to a complete reaction of the carbon matrix with silicon to SiC. The siliconization behaviour and conversion into SiC in dependence of pore morphology and chosen precursor is analysed.At the same time a functional fibre coating has to be developed which protects the fibres from liquid silicon and simultaneously provides a weak fibre matrix bonding. A LPCVD-SiN_x fibre coating has been chosen and is investigated in fibre composites especially in terms of protection and reactivity in different atmospheres during pyrolysis and siliconization.

Specific phenolic resin samples have been developed as the carbon precursor for SiC/C composites. Liquid phenolic resins suitable for fiber-infiltration in the resin transfer moulding (RTM) process are synthesized by using versatile combination of the aromatic component (phenol, naphthalen-2-ol) with various formaldehyde equivalents such as methanal, 1,3,5,7tetraazatricyclo [3.3.1.1^3,7] decane (urotropine), and 1,3,5-trioxane, under different reaction conditions. Room temperature liquid resoles (RTLR) are obtained by using an excess of the formaldehyde component over phenol (≥2) under basic conditions. Upon heating RTLR can form a crosslinked network even without addition of a hardening reagent. In addition, novolacs are synthesized under acidic conditions using a phenol/formaldehyde ratio ≥1. Nitrogen-containing resins contain nitrogen due to reaction of phenol with urotropine. Novolacs and nitrogen-containing resins are solids at room temperature and not self-curing. To infiltrate these both resins into SiC fibers in the RTM process, they are dissolved in 2furanmethanol (furfuryl alcohol FA) and urotropine which is added as curing-agent. Both, the molecular weight and the amount of the dissolved phenolic resin have an influence on the viscosity and the carbon yield after pyrolysis which is important for this application. The aim was to create different phenolic resins for the fabrication in the RTM process and to characterize the carbon after pyrolysis with respect to the structure and porosity as these are key parameters to generate a stoichiometric SiC matrix by LSI.

Twin polymerization is a novel modular approach for the synthesis of hybrid materials. Using this strategy two distinct polymers of either inorganic or organic nature are produced from a single source monomer in a mechanistically coupled process. Twin polymerization is an elegant way for producing nanostructured organic‐inorganic hybrid materials of composition and morphology on demand. The main objective of this Review is the explanation of the principle of various twin polymerization processes and their appropriate terminologies. Different types of twin polymerization are classified with respect to the underlying processes as described in individual examples, demonstrating its potential in material synthesis. Prospects of the synthetic methodology of twin polymerization are demonstrated for different molecular structures of twin monomers and the resulting hybrid materials. A comparison with other scenarios for the synthesis of two different polymers within one procedure is included. image

Defect-free microporous carbon layers on graphite can be produced by DABCO-catalyzed twin polymerization of 2,2′-spirobi[4H-1,3,2-benzodioxasiline] in a slurry polymerization and subsequent thermal transformation of the resulting phenolic resin into carbon.