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

Ionizing radiation has been found to be widely applicable in modifying the structure and properties of polymers, and can be used to tailor the performance of either bulk materials or surfaces. Fifty years of research in polymer radiation chemistry has led to numerous applications of commercial and economic importance, and work remains active in the application of radiation to practical uses involving polymeric materials. This paper provides a survey of radiation-processing methods of industrial interest, ranging from technologies already commercially well established, through innovations in the active R&D stage which show exceptional promise for future commercial use. Radiation-processing technologies are discussed under the following categories: cross-linking of plastics and rubbers, curing of coatings and inks, heat-shrink products, fiber–matrix composites, chain-scission for processing control, surface modification, grafting, hydrogels, sterilization, natural product enhancement, plastics recycling, ceramic precursors, electronic property materials, ion-track membranes and lithography for microdevice production. In addition to new technological innovations utilizing conventional gamma and e-beam sources, a number of promising new applications make use of novel radiation types which include ion beams (heavy ions, light ions, highly focused microscopic beams and high-intensity pulses), soft X-rays which are focused, coherent X-rays (from a synchrotron) and e-beams which undergo scattering to generate patterns.

High-energy radiation and polymers: A review of commercial processes and emerging applications

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

This review highlights the synthesis, processing and properties of non-oxide silicon-based ceramic materials derived from silazanes and polysilazanes. A comprehensive summary of the preparation of precursor compounds containing Si–N–Si units, including commercially available materials, is followed by the discussion of various processing techniques. The fabrication of dense bulk ceramics in the Si/E/C/N systems is reported which involves cross-linking of the polymeric ceramic precursor followed by a polymer-to-ceramic transformation step. The cross-linked precursor can be milled, compacted and pyrolysed to form dense, additive-free, amorphous silicon carbonitride monoliths or polycrystalline composites which withstand oxidation in air at 1600°C. Furthermore, an overview is given on the fabrication of silazane derived powders and coatings involving chemical vapour deposition (CVD) methods utilising volatile precursors. Fibre spinning and fibre properties, as well as other processing techniques like infiltration of preforms, the preparation of porous ceramics and joining are briefly discussed. A state of the art of the mechanical properties of polymer derived amorphous Si/C/N and Si/B/C/N ceramics with respect to hardness as well as high-temperature creep and oxidation resistance is summarised. Finally, some important aspects of industrial applications will be considered. The review is in part based on our own work related to the polysilazane derived ceramics, but will also cover a comprehensive state of the art including the published literature in this field.

Silazane derived ceramics and related materials

Manufacturing of bulk ceramic components from materials in the system Si-Me-C-N-O (Me = Ti, Cr, V, Mo, Si, B, CrSi2, MoSi2, etc.) from preceramic organosilicon polymers - such as poly(carbosilanes), poly(silazanes), or poly(siloxanes) - has become possible by incorporating reactive filler particles into the liquid or solid polymer pre-cursor. During pyrolytic decomposition of the polymer matrix, the filler particles react with carbon from the polymer precursor or nitrogen from the reaction gas atmosphere to form new (oxy)carbide or (oxy)nitride phases embedded in a nanocrystalline Si-O-C(-N) matrix. The selective expansion encountered in the filler phase reaction can be used to compensate for the polymer shrinkage upon pyrolytic conversion. The formation of a transient pore net-work between 400° and 1000°C is governed by the polymer decomposition as well as the filler particle reaction kinetics. Thus, the properties of the oxycarbonitride composite materials can be tailored by controlling the microstructures of the polymer-derived matrix phase, the filler network, and the residual porosity. Near-net-shape forming of bulk ceramic components, even with complex geometry, is possible, making novel applications of polymer-derived bulk materials in biomedical, electrical, and mechanical fields highly interesting.

Active‐Filler‐Controlled Pyrolysis of Preceramic Polymers

The structure of polycarbosilane is represented by three structural elements, but their quantification is difficult. Polycarbosilanes were synthesized by three methods and the respective molecular structures were examined by measurements of the molecular weight and the intrinsic viscosity, infrared, ultraviolet,1H-,13C- and29Si-NMR spectral measurements, and chemical analysis. The three structural elements (SiC4, SiC3H, SiCxSi4−x) in the polycarbosilane molecule were determined quantitatively. By the comparison between1H-NMR spectral data and calculation assuming a linear chain structure, the number of linkages in the unit consisting of ten silicon atoms was estimated to be 3 to 4. This result is in agreement with the result from the intrinsic viscosity; it was found that the shape of the polycarbosilane molecule is planar.

Synthesis of continuous silicon carbide fibre: Part 4The structure of polycarbosilane as the precursor

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

A polycarbosilane, the starting material of β-SiC fibers, was prepared without autoclave. The new method is simple and more economical than the previous one. Furthermore, a great number of bundles of SiC fibers were obtained by way of oxidative reactions of polycarbosilane fibers.

SIMPLE SYNTHESIS OF THE CONTINUOUS SiC FIBER WITH HIGH TENSILE STRENGTH

Polycarbosilane fibers were irradiated by gamma-rays under vacuum and by electron beam in He gas flow or under vacuum at room temperature. Free radicals on Si and C atoms were produced. Most radicals reacted with each other, causing cross-links between polycarbosilane molecules. Some radicals, which did not contribute to cross-linking, were fairly stable under vacuum or in inert gas at room temperature but oxidized on exposure to air. The number of stable radicals under vacuum could be decreased by annealing. The remaining radical concentration was about 1% after annealing at 513 K. By a combination of radiation curing and annealing, SiC fibers with smaller quantities of oxygen were prepared. The mechanical properties of the SiC fibers showed a high tensile strength of 2.5 GPa after heat treatment at 1773 K. On the other hand, polycarbosilane fibers could be cured by radiation oxidation at room temperature, that is, gamma-ray or electron irradiation in oxygen, and the oxygen content could be well controlled by irradiation dose and dose rate. The SiC fibers obtained by the radiation oxidation had an oxygen gradient from the surface to the center which was dependent on the radiation oxidation conditions.

Kiyohito Okamura

Papers

Synthesis of continuous silicon carbide fibre: Part 4The structure of polycarbosilane as the precursor

Structural analysis in continuous silicon carbide fiber of high tensile strength

SIMPLE SYNTHESIS OF THE CONTINUOUS SiC FIBER WITH HIGH TENSILE STRENGTH

Application of radiation curing in the preparation of polycarbosilane-derived SiC fibers

Gd3Al5O12 Phase Obtained by Crystallization of Amorphous Gd2O3·5/3Al2O3