Polymer‐Derived Ceramics

Abstract

Polymer‐derived ceramics (PDCs) represent a class of ceramics that are preparatively accessible from inorganic polymers (also called preceramic polymers). The synthesis and processing of PDCs from polymeric precursors have been shown within the past four decades to be an excellent way to design ceramics, which provides unique tools to control and tune structural features and consequently properties in PDCs. Thus, the molecular architecture and the chemistry of the preceramic polymers strongly correlate to the polymer‐to‐ceramic transformation characteristics as well as the structural features of the resulting PDC materials. By carefully designing the preceramic polymer, fine‐tuning of the chemical and phase composition of the resulting ceramics is possible, which results in unique microstructures and behavior thereof. The present article aims to give a brief introduction to the field of PDCs. Typically, an introduction of preparative tools to access PDCs from tailored inorganic polymers will be done. In addition, a critical consideration of the main structural features of PDCs will be given, with emphasis on the strong correlation between the nano/microstructure of the PDCs and the molecular architecture of their polymeric precursors. Also, various technologies being used to process PDCs in the form of porous materials, coatings, fibers, complex‐shaped monolithic parts, and so on will be introduced and discussed. Finally, some selected structural and functional properties (e.g., high‐temperature behavior, electrical properties, optical properties, and bioactivity) of PDCs will be highlighted and some emerging application fields in which PDCs may be highly suitable material candidates will be introduced. The present article does not intend to provide an exhaustive review of the activities from the past three to four decades in the field of PDCs, but rather to give a short overview of the particularities and the potential of this technology. The article refers in the section “Related Papers” to some excellent reviews and book chapters from the past 20 years, which address and summarize various aspects related to PDCs.

Advances in the Synthesis of Preceramic Polymers for the Formation of Silicon-Based and Ultrahigh-Temperature Non-Oxide Ceramics

“…PIP consists of infiltrating a fibrous preform with a liquid preceramic precursor that is subsequently solidified to retain shape and pyrolyzed to convert to a ceramic (Figure ). The infiltration and pyrolysis cycle is repeated several times to obtain a dense matrix microstructure due to the low volumetric yield of PCPs. , The infiltrated preceramic polymer is responsible for holding the three-constituent assembly together and, once converted to ceramic, provides environmental protection to the fiber-reinforcement architecture.…”

“…The infiltration and pyrolysis cycle is repeated several times to obtain a dense matrix microstructure due to the low volumetric yield of PCPs. 1,2 The infiltrated preceramic polymer is responsible for holding the three-constituent assembly together and, once converted to ceramic, provides environmental protection to the fiber-reinforcement architecture.…”

“…Preceramic polymers (PCPs) are macromolecules that form ceramics when heated to sufficient pyrolysis temperatures and are of interest to chemists due to the fundamental synthetic advances needed to create them. Furthermore, PCPs are of practical interest to engineers for their inherent processability as well as the metastable ceramic compositions that they offer. − The unique properties of these ceramic precursors are manifold, including the ability of preceramic macromolecules to be processed with well-established methods and subsequently heat-treated to yield an inorganic replica of the polymer shape. Such combined shaping and firing operations deliver high-performance ceramic fibers or complex ceramic shapes via additive manufacturing .…”

“…Such combined shaping and firing operations deliver high-performance ceramic fibers or complex ceramic shapes via additive manufacturing . PCPs and their polymer-derived ceramics (PDCs) are critical for fabricating high-performance ceramic fibers, composites, and components that will enable future high-speed flight, aerospace propulsion, automotive, and nuclear power applications. ,− Advancement in the field requires a multidisciplinary approach to improve upon existing preceramic polymers.…”

Polymer‐derived SiOC ceramic coating for corrosion protection

“…15 Polymer-derived ceramics (PDCs) have gained good attention in the last two decades as (i) PDCs can be processed at low temperatures to obtain thermochemically stable ceramics, therefore, it resolves the problems of traditional ceramic processing methods, (ii) PDCs can be coated on complex shaped substrates, and (iii) their microstructure can be tuned by changing the precursor composition. [16][17][18][19][20][21] Common silicon-based polymeric precursors are polysilazanes, polycarbosilanes, and polysiloxanes; pyrolysis of these precursors under inert atmosphere leads to the formation of silicon carbonitride (SiCN), silicon carbide (SiC), and silicon oxycarbide (SiOC), respectively. 22 Among these, SiOC ceramics are considered as "All-rounder" due to its applications in advanced functional and structural applications.…”