Polymer Derived Ceramics, Corrosion, Oxidation, Structural Evolution


Polymer-derived ceramics are a new class of materials synthesized by thermal decomposition of polymer precursors. Previous studies have shown that the materials exhibit excellent thermo-mechanical properties and can be stable at temperatures up to 2000oC. Furthermore, the novel polymer-to-ceramics process enables the manipulation of the ceramic structures at the atomic/nano level by designing the chemistry of polymer precursors and controlling the pyrolysis conditions, thereby, the properties of ceramics. In this dissertation, oxidation/hot-corrosion behavior and the structural evolution of Si-Al-C-N ceramics have been studied. The structural evolution and crystallization behavior of the SiCN and SiAlCN ceramics are investigated using FT-IR, XRD, and NMR. The results revealed that aluminum could greatly affect the structural evolution and crystallization behavior of polymer-derived ceramics, resulting to better stability. The oxidation kinetics of the SiCN and SiAlCN ceramics in air is determined by directly measuring the thickness of the oxide scale with SEM as a function of oxidation time. The results revealed that while the oxidation of the SiCN ceramics follows parabolic kinetics in all of the ranges of testing temperatures, oxidation of the SiAlCN ceramics is complicated: their oxidation rates are similar to that of SiCN ceramics at the earlier stage, but they decrease to very low levels after a certain time. The oxidation rate of the SiAlCN ceramics is more than an order of magnitude lower than any other silicon based ceramics previously reported. The transportation behavior of oxygen through the oxide scales is studied by 18O diffusion. The results indicate that oxidation is controlled by molecular oxygen diffusing through the oxides for both SiCN and SiAlCN ceramics; however, the oxygen diffusion rate in the oxides on SiAlCN ceramics is remarkably retarded. The structures of the oxides are characterized by XRD and NMR. A structural model is advanced to account for the aluminum effect on the oxygen diffusion in the oxide. The oxidation and hot-corrosion kinetics of the SiCN and SiAlCN ceramics in water vapor are determined by measuring their weight changes as a function of annealing time. The kinetic constants, kp and kl, are obtained by fitting the weight-change data with a paralinear model. The results reveal that the SiAlCN ceramics have a much better corrosion resistance than the SiCN and CVD SiC/Si3N4. After annealing at 1400oC for 300 hours, the SiAlCN-20 still retains more than 70% of its original strength, while the SiCN only retains about 20% of its original strength. The improvement in oxidation/hot-corrosion resistance of the SiAlCN ceramics is attributed to the low activity of the SiO2 in the Al2O3-containing silica. In summary, I have developed a new class of high-temperature materials, Si-Al-C-N ceramics. It is demonstrated that these new materials have excellent oxidation and corrosion resistance and thermal stability. Together with their easy processability, the materials will find many high temperature applications such as environmental barrier coatings, ceramic matrix composites, and MEMS for harsh environments.


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Graduation Date





An, Linan


Doctor of Philosophy (Ph.D.)


College of Engineering and Computer Science


Mechanical, Materials, and Aerospace Engineering

Degree Program

Materials Science and Engineering








Length of Campus-only Access


Access Status

Doctoral Dissertation (Open Access)