Preceramic polymers (PCPs) are a group of specialty macromolecules
that serve as precursors for generating inorganics, including ceramic
carbides, nitrides, and borides. PCPs represent interesting synthetic
challenges for chemists due to the elements incorporated into their
structure. This group of polymers is also of interest to engineers
as PCPs enable the processing of polymer-derived ceramic products
including high-performance ceramic fibers and composites. These finished
ceramic materials are of growing significance for applications that
experience extreme operating environments (e.g., aerospace propulsion
and high-speed atmospheric flight). This Review provides an overview
of advances in the synthesis and postpolymerization modification of
macromolecules forming nonoxide ceramics. These PCPs include polycarbosilanes,
polysilanes, polysilazanes, and precursors for ultrahigh-temperature
ceramics. Following our review of PCP synthetic chemistry, we provide
examples of the application and processing of these polymers, including
their use in fiber spinning, composite fabrication, and additive manufacturing.
The principal objective of this Review is to provide a resource that
bridges the disciplines of synthetic chemistry and ceramic engineering
while providing both insights and inspiration for future collaborative
work that will ultimately drive the PCP field forward.
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