Polymer-derived ceramics (PDCs) are a unique class of multifunctional materials synthesized by thermal decomposition of polymeric precursors. Due to their unique and excellent properties and flexible manufacturing capability, PDC is a promising technology to prepare ceramic fibers, coatings, composites and micro-sensors for high-temperature applications. However, the structure-property relationships of PDCs have not been well understood. The lack of such understandings drastically limited the further developments and applications of the materials. In this dissertation, the structure and properties of amorphous polymer-derived silicon carbonitride (SiCN) and silicoboron carbonitride (SiBCN) have been studied. The SiCN was obtained using commercially available polysilazane as pre-ceramic precursor, and the SiBCN ceramics with varied Si-to-B ratio were obtained from polyborosilazanes, which were synthesized by the hydroboration and dehydrocoupling reaction of borane and polysilazane. The structural evolution of polymer-derived SiCN and SiBCN ceramics from polymer to ceramics was investigated by NMR, FTIR, Raman, EPR, TG/DTA, and XRD. The results show a phaseseparation of amorphous matrix and a graphitization of “free” carbon phase, and suggest that the boron doping has a great influence on the structural evolution. The electric and dielectric properties of the SiCN and SiBCNs were studied by I-V curves, LCR Meter, and network analyzer. A new electronic conduction mechanism and structure model has been proposed to account for the relationships between the observed properties and microstructure of the materials. Furthermore, the SiBCN ceramics showed the improved dielectric properties at characterization iv temperature up to 1300 ºC, which allows the fabrication of ultrahigh-temperature wireless microsensors for extreme environments.

Les matrices céramiques autocicatrisantes sont constituées d’une alternance de couches de SiC, B-C et Si-B-C, déposées par voie gazeuse (CVD). Les couches borées (Si)-B-C sont amorphes après élaboration et leur structure évolue à haute température (T ≥ 1000 °C). Diverses caractérisations (XRD, spectroscopie Raman, NMR, diffusion des neutrons, XANES) ont permis de préciser la structure locale des céramiques brutes d'élaboration. Celle-ci a par la suite été validée par des simulations par dynamique moléculaire ab initio. Elle est constituée de motifs icosaédriques, similaires à ceux de B4C, mais fautés et reliés entre eux par des environnements tétravalents CB4-xCx et trivalents BC3. Dans le cas des matériaux Si-B-C, cette même phase amorphe forme un continuum incluant des clusters de SiC. L’évolution structurale de ces céramiques sous atmosphère inerte a été étudiée en fonction de la température (1100°C ≤ T ≤ 1400 °C) et du temps (t ≤ 1 h). Le caractère métastable des matériaux induit une cinétique de réorganisation rapide. L'évolution structurale se traduit successivement, à T et t croissants, par l’apparition de carbone libre sp2, la cristallisation de B4C, ainsi que la croissance de nanocristallites de SiC dans les matériaux Si-B-C. Les propriétés mécaniques ont également été caractérisées à haute température à l’aide d’essais sur microcomposites Cf/(Si)-B-Cm. Les matériaux font preuve d’un comportement transitoire complexe et fortement dépendant de la température du fait de leur évolution structurale. / Self-healing matrices are composed of SiC, B-C and Si-B-C multilayers deposited by chemical vapour deposition (CVD). The boron-rich layers (Si)-B-C are amorphous in their as-deposited state but crystallize at high temperature (T ≥ 1000 °C). Various analyses (XRD, Raman spectroscopy, NMR, neutron diffraction, XANES) were used to characterize the local structure of the as-processed and heat-treated ceramics. The local structure of heat-treated ceramics was also confirmed by molecular dynamic ab initio simulations. The structure consists of icosahedral units as in B4C but faulted and connected with each other through tetrahedral CB4-XCX and trigonal BC3 sites. In Si-B-C ceramics, the same amorphous phase forms a continuum embedding SiC clusters. The structural evolution of the ceramics in inert atmosphere were studied as a function of temperature (1100°C ≤ T ≤ 1400 °C) and time (t ≤ 1 h). The metastability of the materials leads to fast kinetics of reorganization. When T and t increase, one observes successively the formation free-sp2 carbon, the crystallization of B4C and, in Si-B-C ceramics, the coarsening of the SiC nanocrystallites. The high temperature mechanical properties have also been assessed by tensile tests on Cf/(Si)-B-Cm microcomposites. The materials undergo a complex transient behaviour which is strongly temperature dependent due to the structural changes.