CERAMIC FIBER PROCESSING

Nicalon and Tyranno ceramic fibers, two well-known preceramic derived commercial products, are marketed for structural applications. Nicalon is a SiC based ceramic fiber processed using chemistry and techniques first developed by Yajima and coworkers [6-14]. Tyranno fibers are SiC/TiC based fibers produced via novel modifications to the original Yajima work [15-17]. Elastic moduli and tensile strengths for both fibers are of the order of 250-300 GPa and 2-3 GPa respectively. Textron s CVD SiC fibers (not preceramic) offer tensile strengths of up to 4 GPa [18]. The elastic modulus of sintered, hot pressed SiC is in the range of 400-450 GPa [19]. These compare with tensile strengths of =< 8 GPa and an elastic modulus of= 580 GPa for single crystal, SiC whiskers [18]. 

Surface combustion devices are designed for fully premixing the gaseous fuel and air and burning it on a porous radiant surface. The close coupling of the combustion process with the burner surface results in low flame temperatures and, consequently, low NO formation. Surface materials can include ceramic fibers, reticulated ceramics, and metal alloy mats. This approach allows the burner shape to be customized to match the heat transfer profile with the application. 

Scholtz, J. H., et al., High Performance Ceramic Fibers by CVD TQchnologyC Materials and Manufacturing Processes, 6(3) (1991)... 

The cyclotrisilazane (R = Me) produced in reaction (14) is recycled at 650°C [by reaction with MeNHo) the reverse of reaction (14)] to increase the yield of processible polymer. Physicochemical characterization of this material shows it to have a softening point at 190°C and a C Si ratio of 1 1.18. Filaments 5-18 pm in diameter can be spun at 315°C. The precursor fiber is then rendered infusible by exposure to air and transformed into a ceramic fiber by heating to 1200°C under N2- The ceramic yield is on the order of 54% although, the composition of the resulting amorphous product is not reported. The approach used by Verbeek is quite similar to that employed by Yajima et al. (13) in the pyrolytic preparation of polycarbosilane and its transformation into SiC fibers. 

The first useful organosilicon preceramic polymer, a silicon carbide fiber precursor, was developed by S. Yajima and his coworkers at Tohoku University in Japan [5]. As might be expected on the basis of the 2 C/l Si ratio of the (CH3)2SiCl2 starting material used in this process, the ceramic fibers contain free carbon as well as silicon carbide. A typical analysis [5] showed a composition 1 SiC/0.78 C/0.22 Si02- (The latter is introduced in the oxidative cure step of the polycarbosilane fiber). 

The spun polysilane fibers are cured by oxidation in air at a temperature of 160 - 200°C. The curing process is necessary to permit the conversion of the green fiber to the ceramic fiber without softening during pyrolysis. It is presumed that the oxidation mechanism results in the formation of Si-O-C and Si-O-Si bonds by the reaction of Si-CH3 and Si-Si in the polysilane. 

Fig. 8 Fundamental production process of SiC-based ceramic fiber using a polycarbosilane...

The other process is the transformation of an organic precursor into a continuous thin ceramic fiber. In the spinning process, polycarbosilane, a high molecular weight polymer containing Si and C, is obtained by thermal decomposition and polymerization of polydimethylsilane. The fiber thus produced consists of a mixture of P-SiC, carbon crystallite and SiO. The presence of carbon crystallite suppresses the growth of SiC crystals. Yajima and coworkers (Yajima et al., 1976, 1978, 1979) were the first to produce fine (10-30 pm in diameter), continuous and flexible fibers, which are commercialized with the trade name of Nicalon (Nippon Carbon Co.). 

Solution chemistry remains attractive as an inexpensive technique useful for processing ceramics, fibers or coatings, even on a large scale not possible with evaporation techniques. However, the application of these solution techniques to multicomponent systems has rarely been attempted. A better basic understanding of all reaction steps from the solution to the ceramic is needed before a real improvement in the process will be possible. 

As noted earlier, CVl is nsed primarily to form ceramic-fiber-reinforced ceramic matrix composites. The most common of these combinations is SiC fiber/SiC matrix composites. One commercially available product has a two-dimensional 0/90 layup of plain weave fabric and fiber volume fraction of about 40%. This same composite can be fabricated with unidirectional fibers and with 45° architectures. The most commonly used SiC fiber for the preforms is Nicalon , the mechanical properties for which were provided earlier in Section 5.4.2.7. A number of other carbide and nitride fibers are also available, including Si3N4, BN, and TiC. Preform geometries can be tailored to the application in order to maximize strength and toughness in the direction of maximnm stresses. The reactions used to form the matrix are similar to those used in CVD processes (cf. Section 7.2.4) and those described previously in Eq. (3.105). 

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