Polymer derived ceramic composites as environmental barrier coatings on steel

Polymer derived ceramics have shown promise as a novel way to process low-dimensional ceramics such as fibers and coatings. They offer advantages over traditional ceramic processing routes including lower pyrolysis temperatures and the ability to employ polymeric processing techniques. The main drawback to preceramic polymers is that they undergo a shrinkage during pyrolysis that can be greater than 50-volume%. One way to overcome this shrinkage is to add filler particles, usually elemental or binary metals, which will expand upon reaction with the pyrolysis atmosphere, thereby compensating for the shrinkage of the polymer. The aim of this study is to develop a polymer derived ceramic composite coating on steel as a barrier to oxidation and carburization, while concurrently gaining insight as to the fundamental mechanisms for compositional and microstructural evolution within the system. A systematic approach to selecting the preceramic polymer and expansion agents was taken. Six commercially available poly(silsesquioxane) polymers and a polysiloxane were studied. Several metals and an intermetallic were considered as potential expansion agents. The most desirable polymer/expansion agent combination was achieved with poly(hydridomethylsiloxane) as the matrix and titanium disilicide as the filler. Processing parameters have been optimized and a relationship derived to predict final coating thickness based on slurry viscosity and dip coating withdrawal speed. Microstructural analysis reveals an amorphous composite coating of oxidized filler particles in a silica matrix. A diffusion layer is visible at the coating-steel interface, indicating good bonding. The optimized coatings are ∼18mum thick, have some residual porosity and a density of 2.57g/cm3. A systematic study of the phase transformations and microstructural changes in the coating and its components during pyrolysis in air is also presented. The system evolves from a polymer filled with a binary metal at room temperature, to an inorganic amorphous network of oxidized silicon and titanium at the optimized processing temperature of 800°C. The polymer-to-ceramic conversion occurs between 400°C and 600°C where the last of the organics are evolved, the expansion agent begins to oxidize, and the composite densities. Finally, results of mechanical testing and both cyclic and static oxidation testing are discussed.