Abstract
Preceramic polymers have been proposed in the late fifty’s as non-oxide silicon based ceramic precursors generally called PDCs for “Polymer Derived Ceramics”. Compared to traditional synthesis ways, the PDCs route can offer many advantages in terms of compositions, structures and textures of ceramics. Due to its intrinsic properties (thermal, chemical and mechanical resistance, semi-conductor behavior,...), silicon carbide (SiC) and their derivatives with nitrogen (silicon carbonitride, SiCN) can be considered as one of the best materials for the next generation of ceramic based membranes, in particular in the hydrogen production processes (from CO2, CH4 or through the water gas shift reaction for example). By investigating the PDCs route, a hydrophobic and amorphous SiC material suitable for hydrogen separation process exhibiting good permeability/selectivity ratio, high thermal mechanical and chemical resistance coupled with a good stability under wet atmosphere up to 500°C can be proposed. However, the use of preceramic polymrers induces an important dimensional modification during the pyrolysis allowing the conversion from polymer to ceramic. Residual stresses caused by the volume shrinkage leads to the formation of cracks or even collapses of the structure of shaped preceramic polymers. This study is focused on the elaboration of SiC based macroporous substrates or microcellular foams, mesoporous and microporous coatings in the aim to propose a SiC based material showing a hierarchized porosity dedicated to gaseous separation applications. The AllylHydridoPolycarbosilane (AHPCS) is used as SiC precursor. After the chapters I and II, respectively dedicated to a literature review and the materials and methods used, two strategies are enforced in the chapters III and IV to generate these materials with a better control of the polymer dimensional change. In the first strategy (chapter III), passive (nanodiamonds) and active (boron particles) fillers are introduced in the AHPCS to generate some formulations with different fillers proportions and opposing to the volume shrinkage of the polymer during the pyrolysis and create composite materials. In the second strategy (chapter IV), a single molecular source approach consisting of the introduction of boron at the molecular state in the AHPCS is proposed. This introduction of boron leads to increase the ceramic yield and to reduce the mass loss of the modified AHPCS during the pyrolysis. In the chapters III and IV, monolithic dense structures are developed to better understand the dimensional change occurring during the pyrolysis. Synthetized and selected formulations and polymers will serve as precursors for macroporous, mesoporous and microporous materials in the chapter V.