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High Yield Polycarbosilane Precursors to Stoichiometric SiC.Synthesis, Pyrolysis and Application

Published online by Cambridge University Press:  21 February 2011

Leonard. V. Interrante ,
C.W. Whitmarsh ,
W. Sherwood ,
H.-J. Wu ,
R. Lewis  and
G. Maciel
Leonard. V. Interrante
Affiliation:
Department of Chemistry, Rensselaer Polytechnic Institute, Troy, NY 12180–3590
C.W. Whitmarsh
Affiliation:
Starfire Systems, Inc, P.O. Box 2628, Glenville, NY 12302
W. Sherwood
Affiliation:
Starfire Systems, Inc, P.O. Box 2628, Glenville, NY 12302
H.-J. Wu
Affiliation:
Department of Chemistry, Rensselaer Polytechnic Institute, Troy, NY 12180–3590 current address: SRI International, 333 Ravenswood Ave., Meno Park, CA 94025
R. Lewis
Affiliation:
Department of Chemistry, Colorado State University, Fort Collins, CO 80523
G. Maciel
Affiliation:
Department of Chemistry, Colorado State University, Fort Collins, CO 80523
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Abstract

The synthesis and properties of two polycarbosilanes that have essentially a “SiH2CH2” composition is described. One of thesepolymers is a highly branched hydridopolycarbosilane (HPCS) derived fromGrignard coupling of CI3SiCH2CI followed by LiAIH4 reduction. This synthesis is amenable to large scaleproduction and we are exploring applications of HPCS as a source of SiCcoatings and its allyl-derivative, AHPCS, as a matrix source for SiC- andC-fiber-reinforced composites. These polymers thermoset on heating at200-400 °C (or at 100 °C with a catalyst) and give near stoichiometric SiCwith low O content in ca. 80% yield on pyrolysis to 1000 °C. The secondmethod involves ring-opening polymerization of1,1,3,3-tetrachlorodisilacyclobutane and yields a high molecular weight,linear polymer that can be reduced to [SiH2CH2]n (PSE), the monosilicon analogof polyethylene. In contrast to high density polyethylene which melts at 135°C, PSE is a liquid at room temperature which crystallizes at ca. 5 °C. Onpyrolysis to 1000 °C, PSE gives stoichiometric, nanocrystalline, SiC invirtually quantitative yield. The polymer-to-ceramic conversion was examinedfor PSE by using TGA, mass spec, solid state NMR, and IR methods yieldinginformation regarding the cross-linking and structural evolution processes.The results of these studies of the polymer-to-ceramic conversion processand our efforts to employ the AHPCS polymer as a source of SiC matrices aredescribed.

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Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 346: Symposium N – Better Ceramics Through Chemistry VI , 1994 , 595
Copyright
Copyright © Materials Research Society 1998

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