Ceramic precursors, polysilanes

Other linear polysilanes can also be used as ceramic precursors. Solid objects of silicon carbide are manufactured by Nippon Soda Co. from polysilastyrene and finely divided silicon carbide powder.133 These materials are blended, injection molded to the... 

Applications. Some applications of polysilanes include their use as semiconductors, photoresists, photoinitiators, nonlinear optical materials, and ceramic precursors (9). Their use as ceramic precursors can be illustrated by the following reactions ... 

Two types of new silicon-branched organosilicon polymers, linear and ladder polysilane structures, were produced from dihalo- and tetrahalodisilane, respectively, via alkali-metal-mediated reactions. Further investigations disclosed that the polymers may he useful as photoresists, semiconductors, ceramic precursors, and composite materials in high-technology fields. 

SiC fibers were produced using polycarbosilanes by Yajima et al. in 1975 [1,2]. Besides SiC fibers, Si-Ti-C-O fibers prepared from a polytitanocarbosi-lane have been obtained by adding a titanium tetrabutoxide to polycarbosilane or polysilane [3]. SiC fibers (Nicalon) and Si-Ti-C-O fibers (Tyranno) are manufactured on an industrial scale. Colorless silicon oxynitride fibers and silicon nitride fibers [4] have been obtained by the nitridation of polycarbosilanes in the author s laboratory. Polymers used for ceramic precursor and the resulting ceramic fibers are listed in Table 1. 

The catalytic dehydrogenation route yields novel polysilanes with Si—H functionalities, which are of interest as ceramic precursors (36). In addition, it has been shown that a variety of new side groups can be introduced using a derivatization approach (eq. 10) (37). 

P. Larcey. 21st NATAS Conference 1992. The Use of Hyphenated TA-MS in the Study of the Pyrolysis of Polysilane Ceramic Precursor. 

A) The coupling of 7t-conjugation in polyacetylene (and related poly-phenylenevinylenes) and cr-conjugation in polysilanes to produce hybrid materials with potentially new or superior optical or optoelectronic properties, and/or to generate efficient ceramic precursors, has been an important... 

Zeigler, J. M. and F. W. G. Fearon (eds.), Silicon-Based Polymer Science A Comprehensive Resource , ACS, Washington, DC, 1990. A reference volume that covers silicones, polysilanes, ceramic precursor polymers, polymers with pendant silicon and silicon-based supramolecular structures. 

The history and development of polysilane chemistry is described. The polysilanes (polysilylenes) are linear polymers based on chains of silicon atoms, which show unique properties resulting from easy delocalization of sigma electrons in the silicon-silicon bonds. Polysilanes may be useful as precursors to silicon carbide ceramics, as photoresists in microelectronics, as photoinitiators for radical reactions, and as photoconductors. 

Possible ways in which polysilanes may be useful include, 1. As precursors to silicon carbide ceramics 2. As photoinitiators in radical reactions 3. As photoconductive materials, and 4. As photoresists in microelectronics. The last of these uses will be treated in the chapter by Miller,(31) and so will not be covered here. 

Soluble polysilane polymers can also be used as precursors to silicon carbide. The first such application, using (PhMeSi)n-(Me2Si)m copolymers ("Polysilastyrene"), was to strengthen silicon nitride ceramics. The Si3N4 ceramic body was soaked in polysilane and refired, leading to the formation of silicon carbide whiskers in the pore spaces and a consequent increase in strength. (U)... 

A rapidly increasing number of publications on polysilanes documents current interest in these polymers (JJ. Polysilanes are potentially applicable in microlithography as high resolution UV-resists (2J, imageable etch barriers ), or contrast enhancement layers (4). They have been successfully used as precursors to Si-C fibers (5J and ceramic reinforcing agents ((L). Polysilanes have also initiated polymerization of vinyl monomers (J ). Doping of polysilanes have increased their conductivity to the level of semiconductors (8). Very recently polysilanes were used as photoconductors (9) and non-linear optical materials (10b... 

The spectrum of silicon based polymers is enriched by high tech ceramics like silicon nitride and carbide, respectively. These materials are produced by pyrolysis of appropriate polymeric precursors such as polysilanes, polycarbosilanes and polysilazanes (preceramics). These synthetic ceramics display a certain analogy to silicates, having SiC, SiN, or Si(C,N) as structural subunits instead ofSiO. 

Soluble polysilane derivatives (I) represent a new class of radiation sensitive materials for which a number of new applications have recently appeared. In this regard, they have been utilized as (i) thermal precursors to ceramic materials (2,3) ... 

Polysilanes can be regarded as one-dimensional analogues to elemental silicon, on which nearly all of modern electronics is based. They have enormous potential for technological uses [1-3]. Nonlinear optical and semiconductive properties, such as high hole mobility, photoconductivity, and electrical conductivity, have been investigated in some detail. However, their most important commercial use, at present, is as precursors to silicon carbide ceramics, an application which takes no advantage of their electronic properties. 

Research and development in the field are still continuing at a fast pace, particulady in the area of absorption and emission characteristics of the polymers. Several reasons account for this interest. First, the intractable poly dime thylsilane [30107-43-8] was found to be a precursor to the important ceramic, silicon carbide (86—89). Secondly, a number of soluble polysilanes were prepared, which allowed these polymers to be studied in detail (90—93). As a result of studies with soluble polymers it became clear that polysilanes are unusual in their backbone CT-conjugation, which leads to some very interesting electronic properties. 

For some uses it is important to form bonds that link different polysilane chains, to transform soluble, meltable polysilanes into insoluble resins. This process is vital if the polysilanes are to be used as precursors to silicon carbide ceramics, since, if cross-linking is not carried out, most of the polymer is volatilized before thermolysis to silicon carbide can take place. Several methods have therefore been developed to bring about cross-linking of polysilanes.109 110... 

Preparative organosilicon chemistry offers manifold possibilities for the synthesis of precursors for nonoxide ceramics (Scheme 18.1). The focus has been on the synthesis of polymers such as polysilanes A, polysilazanes B, polycarbosilanes... 

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