Preceramic polymers were proposed over 30 years ago as precursors for the fabrication of mainly Si-based advanced ceramics, generally denoted as polymer-derived ceramics (PDCs). The polymer to ceramic transformation process enabled significant technological breakthroughs in ceramic science and technology, such as the development of ceramic fibers, coatings, or ceramics stable at ultrahigh temperatures (up to 2000°C) with respect to decomposition, crystallization, phase separation, and creep. In recent years, several important advances have been achieved such as the discovery of a variety of functional properties associated with PDCs. Moreover, novel insights into their structure at the nanoscale level have contributed to the fundamental understanding of the various useful and unique features of PDCs related to their high chemical durability or high creep resistance or semiconducting behavior. From the processing point of view, preceramic polymers have been used as reactive binders to produce technical ceramics, they have been manipulated to allow for the formation of ordered pores in the meso-range, they have been tested for joining advanced ceramic components, and have been processed into bulk or macroporous components. Consequently, possible fields of applications of PDCs have been extended significantly by the recent research and development activities. Several key engineering fields suitable for application of PDCs include high-temperature-resistant materials (energy materials, automotive, aerospace, etc.), hard materials, chemical engineering (catalyst support, food- and biotechnology, etc.), or functional materials in electrical engineering as well as in micro/nanoelectronics. The science and technological development of PDCs are highly interdisciplinary, at the forefront of micro- and nanoscience and technology, with expertise provided by chemists, physicists, mineralogists, and materials scientists, and engineers. Moreover, several specialized industries have already commercialized components based on PDCs, and the production and availability of the precursors used has dramatically increased over the past few years. In this feature article, we highlight the following scientific issues related to advanced PDCs research: (1) General synthesis procedures to produce silicon-based preceramic polymers.
(2) Special microstructural features of PDCs.
(3) Unusual materials properties of PDCs, that are related to their unique nanosized microstructure that makes preceramic polymers of great and topical interest to researchers across a wide spectrum of disciplines.
(4) Processing strategies to fabricate ceramic components from preceramic polymers.
(5) Discussion and presentation of several examples of possible real-life applications that take advantage of the special characteristics of preceramic polymers. Note: In the past, a wide range of specialized international symposia have been devoted to PDCs, in particular organized by the American Ceramic Society, the European Materials Society, and the Materials Research Society. Most of the reviews available on PDCs are either not up to date or deal with only a subset of preceramic polymers and ceramics (e.g., silazanes to produce SiCN-based ceramics). Thus, this review is focused on a large number of novel data and developments, and contains materials from the literature but also from sources that are not widely available.

Polymer-Derived Ceramics: 40 Years of Research and Innovation in Advanced Ceramics

Handbook of SiC properties for fuel performance modeling

The graphite die set in spark plasma system (SPS) is heated by a pulse direct current. Weak plasma, discharge impact, electric field and electric current, which are based on this current, induce good effects on materials in the die. The surface films of aluminum and pure WC powders are ruptured by the spark plasma. Pure AlN powder is sintered without sintering additives in the electric field. The spark plasma leaves discharge patterns on insulators. Organic fibers are etched by the spark plasma. Thermosetting polyimide is consolidated by the spark plasma. Insoluble polymonomethylsilane is rearranged into the soluble one by the spark plasma. A single crystal of CoSb3 is grown from the compound powders in the electric field by slow heating. Coupled crystals of eutectic powder are connected with each other in the electric field.

Sintering, consolidation, reaction and crystal growth by the spark plasma system (SPS)

Accident tolerant fuel cladding development: Promise, status, and challenges

MUCH work has been done on preparing heat-resistant silicon carbide materials in fibrous form, since plastics or metals can be reinforced with them to obtain very heat-resistant material of great mechanical strength. SiC whiskers1 are, however, impractical because of their shortness (several mm), their non-uniform diameter and high cost of production. SiC-on-W (ref. 2) and SiC-on-C (ref. 3) filaments have been produced by chemical vapour methods. These coated filaments are more expensive, and the treatment for making such composite materials requires careful control. We report here on the synthesis of continuous β-SiC fibres by a new process: the conversion of organometallic polymers to inorganic substances. We have studied the transformation process and the structure and mechanical properties of these fibres.

Development of a silicon carbide fibre with high tensile strength

Continuous silicon carbide fiber of high-tensile strength (about 350 Kg/mm2) was synthesized by means of the heat-treatment of organosilicon polymer obtained from dodecamethylcyclohexasilane. X-ray analysis and high voltage electron microscopic observations revealed that the obtained continuous fiber is an ultrafine grain structure of β-silicon carbide.

Continuous silicon carbide fiber of high tensile strength

Continuous Sic fibers with a tensile strength of 350 kg/mm2 and a Young's modulus of 30 tons/mm2 were synthesized from an organometallic polymer. Continuous fibers were first obtained by heat-treating a polycarbosilane polymer which had been synthesized from dimethyldichlorosilane. The fiber, which contains ultrafine-grain crystallites of β-Sic, has no fiber texture measurable by X-ray diffraction and high-voltage electron microscopy.

Synthesis of Continuous Sic Fibers with High Tensile Strength

The starting material of a continuous silicon carbide fiber with very high tensile strength is a polycarbosilane. It begins to decompose from 300°C in vacuum and is gradually converted into a β-silicon carbide fiber by the heat-treatment at the temperature above 800°C.

Structural analysis in continuous silicon carbide fiber of high tensile strength

WE have previously reported successful production of a high-strength continuous SiC fibre1–3, a high flexural strength SiC sintered body4 and a heat-resistant Fe–Cr alloy5 by converting organometallic polymer polycarbosilane (PC) as the binder to an inorganic in thermal decomposition. We then found that in the thermal decomposition of organometallic polymers such as PC, an amorphous state exists before formation of the (SiC) fine particles; this SiC amorphous state is hardly possible in inorganic reactions. The process of thermal decomposition of organometallic polymers is little known. To obtain general information on the phenomenon, we have newly synthesised multi-element polyborodiphenylsiloxane containing oxygen (B, C, Si, O, H) compared with PC composed of Si, C and H, and observed the process of its thermal decomposition.

Josaburo Hayashi

Papers

Development of a silicon carbide fibre with high tensile strength

Continuous silicon carbide fiber of high tensile strength

Synthesis of Continuous Sic Fibers with High Tensile Strength

Structural analysis in continuous silicon carbide fiber of high tensile strength

Pyrolysis of a polyborodiphenylsiloxane