Silicon pyrolysis

A great potential for new compounds is provided by structures with two carbon and two silicon atoms around the central silicon. These polysilanes with organic groups lead to silicon-carbide ceramics. A wide field of application would be opened up if one could make a polysilane as a plastic mass which could be extruded and modeled and if after pyrolysis silicon-carbide is formed without a strong contraction (this means a high ceramic yield). Polysilane fibers are only one product in a range of many... 

Turning now to other types of ceramic fibre, the most important material made by pyrolysis of organic polymer precursors is silicon carbide fibre. This is commonly made from a poly(diorgano)silane precursor, as described in detail by Riedel (1996) and more concisely by Chawla (1998). Silicon nitride fibres are also made by this sort of approach. Much of this work originates in Japan, where Yajima (1976) was a notable pioneer. 

The first type of polycarbosilane synthesized by using ADMET methodology was a poly[carbo(dimethyl)silane].14c Linear poly(carbosilanes) are an important class of silicon-containing polymers due to their thermal, electronic, and optical properties.41 They are also ceramic precursors to silicon carbide after pyrolysis. ADMET opens up a new route to synthesize poly(carbosilanes), one that avoids many of the limitations found in earlier synthetic methods.41... 

Wu, H. D., and Ready, D. W., Silicon Carbide Powders by Gaseous Pyrolysis of Tetramethylsilane, mSilicon Carbide 87, Ceramic Transactions, 2 35-46 (1987)... 

While the decomposition of silacyclobutanes as a source of silenes has continued to be studied in the last two decades, the interest has largely focused on mechanisms and kinetic parameters. However, a few reports are listed in Table I of the presumed formation of silenes having previously unpublished substitution patterns, prepared either thermally or photo-chemically from four-membered ring compounds containing silicon. Two cases of particular interest involve the apparent formation of bis-silenes. Very low-pressure pyrolysis of l,4-bis(l-methyl-l-silacyclobutyl)ben-zene94 apparently formed the bis-silene 1, as shown in Eq. (2), which formed a high-molecular-weight polymer under conditions of chemical vapor deposition. 

Another process for silicon carbide fibers, developed by Verbeek and Winter of Bayer AG [45], also is based on polymeric precursors which contain [SiCH2] units, although linear polysilmethylenes are not involved. The pyrolysis of tetramethylsilane at 700°C, with provision for recycling of unconverted (CHg Si and lower boiling products, gave a polycarbosilane resin, yellow to red-brown in color, which was soluble in aromatic and in chlorinated hydrocarbons. Such resins could be melt-spun but required a cure-step to render them infusible before they were pyrolyzed to ceramic... 

In the area of preceramic polysilazanes, sufficient progress has been made to produce precursors for silicon nitride fibers, coatings and as binders for silicon nitride powder. However, particular problems still remain to be solved particularly with regard to reducing impurity levels and improving densification during pyrolysis. 

In the design of preceramic polymers, achievement of the desired elemental composition in the ceramic obtained from them (SiC and Si3N4 in the present cases) is a major problem. For instance, in the case of polymers aimed at the production of SiC on pyrolysis, it is more usual than not to obtain solid residues after pyrolysis which, in addition to SiC, contain an excess either of free carbon or free silicon. In order to get close to the desired elemental composition, two approaches have been found useful in our research (1) The use of two comonomers in the appropriate ratio in preparation of the polymer, and (2) the use of chemical or physical combinations of two different polymers in the appropriate ratio. 

These polymers may be used in the preparation of quite pure silicon nitride if the pyrolysis is carried out in a stream of ammonia (a reactive gas) rather than under nitrogen or argon. The ammonia reacts with the... 

The ceramic products obtained in the pyrolysis of the "combined" polymers have not been studied in detail, but some of them have been analyzed for C, N, and Si. The compositions of the ceramic materials obtained cover the range 1 Si3N4 + 3.3 to 6.6 SiC + 0.74 to 0.85 C. Thus, as expected, they are rich in silicon carbide and the excess Si which is obtained in the pyrolysis of the [(CH3SiH)x(CH3Si)y]n materials alone is not present, so that objective has been achieved. By proper adjustment of starting material ratios, we find that the excess carbon content can be minimized [11]. 

On heating in air at 10°C per min, poly(m-carborane-siloxane) shows typically only 4% mass loss at 450°C and 7% mass loss at 600°C (see Fig. 4). In comparison, siloxanes without carborane units, show an approximate 50% mass loss at 450°C. As a consequence of the relatively high boron and carbon content of these materials, pyrolysis is expected to generate ceramic residues of boron carbide/silicon carbide. 

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. 

In our research at MIT we have found transition metal chemistry a very useful aid in the preparation of silicon-containing ceramics by the polymer pyrolysis procedure. 

These problems, low ceramic yield and formation of substantial amounts of elemental silicon in the pyrolysis, can be dealt with in a number of ways. Transition metal-catalyzed cross-linking has been found to be particularly effective [12]. 

Summary A brief review of the preparation of silicon containing preceramic polymers to prepare silicon carbide and silicon carbonitride fibers is given. Methylchlorodisilanes are converted to polysilanes and polysilazanes which yield ceramic fibers after meltspinning, curing, and pyrolysis. 

The polysilazanes were also melt spun, cured, and pyrolyzed to give silicon carbonitride fibers (Eq. 7). The carbon content of these fibers depends on the molecular composition of the polysilazane and the pyrolysis gas. When ammonia is used as reactive gas pure silicon nitride fibers will be obtained (Eq. 8) [14]. 

Polysilazane fibers are rendered infusible by humidity or in the absence of oxygen by ammonia. The final step of producing ceramic fibers is the pyrolysis. The cured fibers are heated at 1200 -1300°C in argon, nitrogen, or in vacuo, and SiC- or SiC/SijN fibers with a diameter of around 15 /xm are obtained. Heating up silicon-polymers, whether polysilanes or polysilazanes, results in the evolution of CH4 and H2. 

Silicone paints are formed by controlled hydrolysis and condensation of alkyl alkox-ysilanes, and may be encountered either alone or in formulations with other synthetic resins. The typical structural unit in the polymer chain is dimethyl siloxane, and pyrolysis of such resins takes place with random chain scission and the extended formation of stable cyclic fragments. In Figure 12.14 the pyrogram of a silicone resin is shown, with cyclic siloxane oligomers eluting at the shorter retention times, followed by the linear siloxane fragments. 

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