Abstract
The synthesis and properties of two polycarbosilanes that have essentially a “SiH2CH2” composition is described. One of these polymers is a highly branched hydridopolycarbosilane (HPCS) derived from Grignard coupling of CI3SiCH2CI followed by LiAIH4 reduction. This synthesis is amenable to large scale production and we are exploring applications of HPCS as a source of SiC coatings and its allyl-derivative, AHPCS, as a matrix source for SiC- and C-fiber-reinforced composites. These polymers thermoset on heating at 200–400 °C (or at 100 °C with a catalyst) and give near stoichiometric SiC with low O content in ca. 80% yield on pyrolysis to 1000 °C. The second method involves ring-opening polymerization of 1,1,3,3-tetrachlorodisilacyclobutane and yields a high molecular weight, linear polymer that can be reduced to [SiH2CH2]n (PSE), the monosilicon analog of 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. On pyrolysis to 1000 °C, PSE gives stoichiometric, nanocrystalline, SiC in virtually quantitative yield. The polymer-to-ceramic conversion was examined for PSE by using TGA, mass spec, solid state NMR, and IR methods yielding information regarding the cross-linking and structural evolution processes. The results of these studies of the polymer-to-ceramic conversion process and our efforts to employ the AHPCS polymer as a source of SiC matrices are described.
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S. Yajima, K. Okamura, J. Hayashi, and M. Imura, J. Amer. Ceram. Soc. 59[7–8] 324 (1976)
S. Yajima, Y. Hasegwa, J. Hayashi, and M. Omori, J. Mater. Sci. 13[12] 2569 (1978)
S. Yajima, “Silicon Carbide Fibers”, pp.201–37, in Handbook of Composites, edited by W. Watt and B.V. Perov, North-Holland, Amsterdam, Netherlands, (1985).
K.J. Wynne and R.W. Rice, Ann. Rev. Mater. Sci., 14, 297 (1984)
R.M. Laine and F. Babonneau, Chem. Mater. 5, 260 (1993).
K. Okamura, “Ceramic Fiber and Whisker Requirements to Advanced Structural Inorganic Composite”, pp.19–34 in Advanced Structural Composites, edited by P. Vicenzini, Elsevier Science Publ. B.V., Amsterdam (1991)
J. Lipowitz, Am. Ceram. Soc. Bull. 70[12], 1888 (1991)
T.F. Cooke, J. Amer. Ceram. Soc., 74[12] 2959 (1991).
F.I. Hurwitz, L. Hyatt, J. Gorecki, and L. D’Amore, Ceram. Eng. Sci. Proc. 8, 732 (1987)
F.I. Hurwitz, J.Z. Gyekenyesi, and P.J. Conroy, Ceram. Eng. Sci. Proc. 10, 750 (1989)
H. Zhang, C.G. Pantano, pp. 223-, in Ultrastructure Processing of Advanced Materials, D.R. Uhlmann and D.R. Ulrich, Eds., John Wiley & Sons (1992).
M.P. Borom, W.B. Hillig, R.J. Singh, W.A. Morrison, and L.V. Interrante, “Fiber-Containing Composite”, US Patent No. 5 015 540 (14 May 1991).
R. Naslain and F. Langlais, MRS Sympos. Proc. 20, 145 (1985)
P.J. Lamicq, G.Q. Bernhart, M.M. Dauchier, and J.C. Mace, Am. Ceram. Soc. Bull. 65[2], 336 (1986)
A.J. Caputo, D.P. Stinton, R.A. Lowden, and T.M. Bessman, Am. Ceram. Soc. Bull. 66[2], 368 (1987)
T.M. Bessman, R.A. Lowden, D.P. Stinton, T.L. Starr, J. de Physique, Colloque C5, 229 (1989).
W. Fohey, M. Battison, J. Halada, and T. Nielson, U.S. Government Report No. WL-TR-92-4019, July 1992.
J.R. Strife, J.P. Wesson, and H.H. Streckert, “A Study of the Critical Factors Controlling the Synthesis of Ceramic Matrix Composites from Preceramic Polymers”, US Government Report No. AD-A23 686, December 1990
B.C. Mutsuddy, Ceramics International 13, 41 (1987)
R.P. Boisvert, “Ceramic Matrix Composites via Organometallic Precursors”, M.S. Thesis, Rensselaer Polytechnic Institute, 214 pages (1988).
H-J. Wu and L.V. Interrante, Macromolecules 25, 1840 (1992)
H.-J. Wu and L.V. Interrante, Polymer Preprints 33[2], 210 (1992).
C.K. Whitmarsh, L.V. Interrante, Organometallics 10, 1336 (1991)
C.K. Whitmarsh, L.V. Interrante, “Carbosilane Polymer Precursors to Silicon Carbide Ceramics”, U.S. Patent No. 5 153 295 (6 October 1992);.
C-Y. Yang and L.V. Interrante, Polymer Preprints 33 [2], 152 (1992).
W.R. Schmidt, V. Sukumar, W.J. Hurley Jr., R. Garcia, R.H. Doremus, and L.V. Interrante, J. Amer. Ceram. Soc. 73, 2412 (1990)
W.R. Schmidt, L.V. Interrante, R.H. Doremus, T.K. Trout, P.S. Marchetti, and G.E. Maciel, Chem. Mater. 3, 257 (1991)
L.V. Interrante, W.R. Schmidt, P.S. Marchetti, and Gary E. Maciel, MRS Symp. Proc. 249, 31 (1992)
W.R. Schmidt, P.S. Marchetti, L.V. Interrante, W.J. Hurley, Jr., R.H. Lewis, R.H. Doremus, and G.E. Maciel, Chem. Mater. 4, 937 (1992)
L.V. Interrante, C.K. Whitmarsh, T.K. Trout, and W.R. Schmidt, “Synthesis and Pyrolysis Chemistry of Polymeric Precursors to SiC and Si3N4”, pp. 243–254 in Organometallic Polymers with Special Properties, NATO ASI Series, Series E, Applied Sciences, Vol. 206, Kluwer Academic Publishers, Dordrecht (1992)
L.V. Interrante, W.R. Schmidt, P.S. Marchetti, and Gary E. Maciel, MRS Symp. Proc. 271, 739 (1992).
D.M. Narsavage, L.V. Interrante, P.S. Marchetti, and G. Maciel, Chem. Mater. 3, 721 (1991).
L.V. Interrante, C.L. Czekaj, M.L. Hackney, G.A. Sigel, P.L. Shields and G.A. Slack, MRS Sympos. Proc. 121, 465 (1988)
Czekaj, CL.; Hackney, M.L.; Hurley, W.J., Jr.; Interrante, L.V.; Sigel, G.A.; J. Am. Ceram. Soc. 73, 352 (1990)
W.R. Schmidt, W.J. Hurley, Jr., V. Sukumar, R.H. Doremus, and L.V. Interrante, MRS Sympos. Proc. 171, 79 (1990)
L.V. Interrante, W.J. Hurley, Jr., W.R. Schmidt, D. Kwon, R.H. Doremus, P.S. Marchetti, and G. Maciel, Ceram. Trans. 19, 3 (1991)
W.R. Schmidt, W.J. Hurley, Jr., R.H. Doremus, L.V. Interrante, and P.S. Marchetti, Ceram. Trans. 19, 19 (1991)
L.V. Interrante, W.R. Schmidt, S.N. Shaikh, R. Garcia, P.S. Marchetti, and G. Maciel, pp. 777–787 in “Chemical Processing of Advanced Materials”, Vol. 206, Series E: Applied Sciences, L.L. Hench and J.K. West, eds., J. Wiley and Sons (1992).
Elemental analysis of the 1000 °C HPCS-SiC gave the following results: %C, 27.9; %H, 0.7; %Si, 63.1; %0, 3.49.
Unpublished work of W. Shi, C.-Y. Yang, and L.V. Interrante, Rensselaer Polytechnic Institute.
C-Y. Yang, P. Marchetti, and L.V. Interrante, Polymer Preprints 33 (2), 208 (1992); F. Babonneau, L. Bois, C-Y. Yang, and L.V. Interrante, Chem. Mater. 6, 51 (1994).
“Encyclopedia of Polymer Science and Engineering”, Volume 6, John Wiley & Sons, New York (1986).
Dr. Kennith Smith, GE CRD (private communication).
I.M. Davidson, M.A. Ring, J. Chem. Soc, Faraday Trans. 76, 1520 (1980)
M.A. Ring, H.E. O’Neal, S.F. Rickborn, B.A. Sawray, Organometallics 2, 1891 (1983).
J. Harrod, R. Laine, et al, J. Amer. Ceram. Soc. 74, 670 (1991).
The % theoretical density was calculated from the rule of mixtures, using the relative weights and the published density values for the Nicalon fiber cloth. A value of 2.35g/cm3 was used for the AHPCS-SiC matrix material. This was obtained by direct measurement on a densified pellet of 1000 °C AHPCS-SiC The pellet was prepared by VPIP (8 cycles) starting from a preform derived by hot-pressing (200 °C; 360 kg/cm2) a mixture of finely-ground 1000 °C AHPCS-SiC powder and HPCS as a binder in a pellet press.
duPont de Nemours & Co., Wilmington, DE, Product Data Sheet.
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Interrante, L.V., Whitmarsh, C.W., Sherwood, W. et al. High Yield Polycarbosilane Precursors to Stoichiometric SiC. Synthesis, Pyrolysis and Application. MRS Online Proceedings Library 346, 593–603 (1994). https://doi.org/10.1557/PROC-346-595
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DOI: https://doi.org/10.1557/PROC-346-595