Abstract
The first attempts to introduce carbon into glass date back to 1951. But up until recently, the use of carbon or carbide raw materials, and the oxidation, volatilization and decomposition that accompany high temperature melting, have limited the synthesis of true silicon oxycarbide glasses. Here, the term silicon-oxycarbide refers specifically to a carbon-containing silicate glass wherein oxygen and carbon atoms share bonds with silicon in the amorphous, network structure. Thus, there is a distinction between black glass, which contains only a second-phase dispersion of elemental carbon, and oxycarbide glasses which usually contain both network carbon and elemental carbon. In addition to exploring the unique properties and applications of these glasses, per se, they are also of interest for developing models of the residual amorphous phases in polymer-derived silicon-carbide and silicon-nitride ceramics.
The application of sol/gel techniques to glass synthesis has significantly advanced the development and characterization of silicon oxycarbide glasses. In this approach, alkyl-substituted silicon alkoxides, which are molecular precursors containing oxygen and carbon functionalities on the silicon, can be hydrolyzed and condensed without decomposition or loss of the carbon functional group. A low-temperature (<1000°C) heat-treatment of the gel creates a glassy silicate material whose molecular structure consists of an oxygen/carbon anionic network. In addition, there is always a blackening of the material due to elemental carbon, which forms during pyrolysis and densification of the gel. The nature of the network carbon, and especially the distribution and form of the elemental carbon, are fundamental to the structure and properties of these novel materials. Their chemical and physical characteristics as revealed by NMR, Raman and TEM are discussed in the overview. In addition, the high temperature stability of these glasses (up to 1750°C), and the effect of hot-pressing, are described.
It will be shown that the silicon oxycarbide network is stable up to 1000–1200°C. The network carbon is terminated with hydrogen (i.e., CH, =CH2 and –CH3), and with polyaromatic carbon (i.e., nC6Hx) wherein most of the elemental carbon resides. These glasses can be described as molecular composites of polyaromatic graphene-rings dispersed in a silicon oxycarbide network. After heating to temperatures in excess of 1000–1200°C, the oxycarbide network decomposes through the loss of hydrogen, and a two- or three-phase glass-ceramic consisting of nanocrystalline graphite, silicon carbide, and amorphous silica or cristobalite, is created. Some of the properties and applications of these glasses/glass-ceramics for coatings, composites and porous solids are summarized.
Similar content being viewed by others
References
_C.J. Brinker and G.W. Scherer, Sol-Gel Science (Academic Press, San Diego, 1990).
H. Schmidt, Organic modification of the glass structure, J. Non-Cryst. Solids 112, 419–423 (1989).
R. Ellis, Method of making electrically conducting glass and articles made therefrom, U.S. Pat. 2,556,616, June 1951.
_C.F. Smith and W.B. Crandall, Method of making carbon contauning glasses, U.S. Patent No. 3,378,431, 1968.
R. Elmer and H. Meissner, Increase of annealing point of 96% SiO2 glass on incorporation of carbon, J. Am. Ceram. Soc. 59(5), 206–209 (1976).
J. Homeny, G. Nelson, and S. Risbud, Oxycarbide glasses in the Mg-Al-Si-O-C system, J. Am. Ceram. Soc. 71(5), 386–390 (1988).
D. Coon, Effect of silicon carbide additions on the crystallization behavior of a magnesia-lithium-alumina-silica system, J. Am. Ceram. Soc. 72(7), 1270–1273 (1989).
R. Pampuch, W.S. Ptak, S. Jonas, and J. Stoch, The nature of Si-O-C phase(s) formed during oxidation of SiC, in Proceedings of the 9th International Symposium on Reactivity of Solids, Cracow, Poland, Sept. 1980, Vol. 2 (Elsevier, New York, 1980), pp. 674–677.
V.A. Lavrenko, S. Jonas, and R. Pampuch, Petrographic and X-ray identification of phases formed by oxidation of silicon carbide, Ceram. Int. 2, 75–76 (1981).
A.L. Yurkov and B.I. Polyak, Contact phenomenon and interactions in the system SiC-SiO2-RxOy in condensed matter, J. Mater. Sci. 31(10), 2729–2733 (1996).
J. Lipowitz, H.A. Freeman, R.T. Chen, and E.R. Prack, Composition and structure of ceramic fibers prepared from polymer precursors, Adv. Ceram. Mater. 2(2), 121–128 (1987).
J. Lipowitz, Polymer derived ceramic fibers, Ceram. Bull. 70(12), 1888–1894 (1991).
L. Porte and A. Satre, Evidence for silicon oxycarbide phase in Nicalon silicon carbide fiber, J. Mat. Sci. 24(27), (1989).
D.A. White, S.M. Oleff, R.D. Boyer, P.A. Budinger, and J.R. Fox, Preparation of silicon carbide from organosilicon gels: I, synthesis and characterization of precursor gels, Adv. Ceram. Mater. 2(1), 45–52 (1987).
D.A. White, S.M. Oleff, R.D. Boyer, P.A. Budinger, and J.R. Fox, Preparation of silicon carbide from organosilicon gels: II, gel pyrolysis and SiC characterization, Adv. Ceram. Mater. 2(1), 53–59 (1987).
G. Wei, C. Kennedy, and L. Harris, Synthesis of sinterable SiC powders by carbothermic reduction reaction of gel-derived precursor and pyrolysis of polycarbosilane, Ceramic Bulletin 63(8), 1054–1061 (1984).
Krishan L. Luthra, Thermochemical analysis of the stability of continuous “SiC” Fibers, J. Am. Ceram. Soc. 69(10), C-231–C-233 (1986).
M. Nagamori, J.A. Boivin, and A. Claveau, Thermodynamic stability of silicon oxycarbide (Nicalon), J. Mater. Sci. 30, 5449–5456 (1995).
P. Rocabois, C. Chatillon, and C. Bernard, Mass spectrometry experimental investigation and thermodynamic calculation of the Si-C-O system and SixCyOz fibre stability, in Proc. 6th European Conf. on Composite Materials, edited by R. Naslaun et al. (Woodhead Publishing, 1993), pp. 93–100.
P. Rocabois, C. Chatillon, and C. Bernard, Multiple Knudsen cell mass spectrometric investigation of the evaporation of silicon oxycarbide glass, Surface and Coating Techn. 61(86), (1993).
F.K. Chi, Carbon-contauning monolithic glasses via the sol-gel process, Ceram. Eng. Sci. Proc. 4, 704–717 (1983).
F. Babonneau, K. Thorne, and J.D. Mackenzie, Dimethyldiethoxysilane/tetraethoxysilane copolymers: Precursors for the Si-C-O System, Chem. Mater. 1, 554–558 (1989).
H. Zhang and C.G. Pantano, Synthesis and characterization of silicon oxycarbide glasses, J. Am. Ceram. Soc. 73(4), 958–963 (1990).
K. Kamiya, T. Yoko, T. Sano, and K. Tanaka, Distribution of carbon particles in carbon/SiO2 glass composites made from CH3Si(OC2H5)3 by the sol-gel method, J. Non-Cryst. 119, 14–20 (1990).
K. Kamiya, T. Yoko, K. Tanaka, and M. Takeuchi, Thermal evolution of gels derived from CH3Si(OC2H5)3 by the sol-gel method, J. Non-Cryst. Solids 121, 182–187 (1990).
G.M. Renlund, S. Prochazka, and R.H. Doremus, Silicon oxycarbide glasses: Part I. preparation and chemistry, part II. structure and properties, J. Mater. Res. 6(12), 2716–2734 (1991).
F.I. Hurwitz, P.J. Heimann, J.Z. Gyekenyesi, J. Masnovi, and X.Y. Bu, Polymeric routes to silicon carbide and silicon oxycarbide CMC, Ceram. Eng. Sci. Proc. 12(7/8), 1292–1303 (1991).
A.K. Singh and C.G. Pantano, The role of Si-H functionality in oxycarbide glasses synthesis, Mat. Res. Soc. Symp. Proc. 271, 795–800 (1992).
F. Babonneau, G.D. Soraru, G. D'Andrea, S. Dire, and L. Bois, Silicon oxycarbide glasses from sol-gel precursors, Mat. Res. Soc. Symp. Proc. 271, 789–794 (1992).
H. Zhang and C.G. Pantano, High temperature stability of oxycarbide glasses, Mat. Res. Soc. Symp. Proc. 271, 783–788 (1992).
H. Zhang and C.G. Pantano, Sol/gel processing of oxycarbide glasses and glass matrix composites, Ultrastructure Processing of Advanced Materials (Wiley, New York, 1992), pp. 223–233.
V. Belot, R.J.P. Corriu, D. Leclercq, P.H. Mutin, and A. Vioux, Organosilicon gels contauning silicon-silicon bonds, precursors to novel silicon oxycarbide compositions, J. Non-Cryst. 144, 287–297 (1992).
V. Belot, R.J.P. Corriu, D. Leclercq, P.H. Mutin, and A. Vioux, Thermal reactions occurring during pyrolysis of cross-linked polysilazane gels, precursors to silicon oxycarbide glasses, J. Non-Cryst. 147/148, 52–55 (1992).
F. Babonneau, L. Bois, and J. Livage, Silicon oxycarbide via sol-gel route: Characterization of the pyrolysis process, J. Non-Cryst. 147/148, 280–284 (1992).
M. Hammond, E. Breval, and C.G. Pantano, Microstructure and viscosity of hot-pressed silicon oxycarbide glasses, Ceram. Eng. Sci. Proc. 14(9/10), 947 (1993).
P. Colombo, T.E. Paulson, and C.G. Pantano, Conversion of silicone resin to silicon (oxy)carbide, Ceram. Acta. 3, 13–21 (1993).
L. Bois, J. Maquet, F. Babonneau, H. Mutin, and D. Bahloul, Structural characterization of sol-gel derived oxycarbide glasses. 1. Study of the pyrolysis process, Chem. Mater. 6, 796–802 (1994).
E. Breval, M. Hammond, and C.G. Pantano, Nanostructural characterization of silicon oxycarbide glasses and glassceramics, J. Amer. Ceram. Soc. 77(11), 3012–3018 (1994).
V. Belot, R.J.P. Corriu, D. Leclercq, P.H. Mutin, and A. Vioux, Silicon oxycarbide glasses with low O/Si ratio from organosilicon precursors, J. Non-Cryst. Solids 176, 33–44 (1994).
C. Liu, H. Zhang, S. Komarneni, and C.G. Pantano, Porous silicon oxycarbide glasses from organically modified silica gels of high surface area, J. Sol-Gel Science and Techn. 1, 141 (1994).
L. Bois, J. Maquet, F. Babonneau, and D. Bahloul, Structural characterization of the sol-gel derived oxycarbide glasses. 2._Study of the thermal stability of the silicon oxycarbide phase, Chem. Mater. 7, 975–981 (1995).
G.D. Soraru, G. D'Andrea, R. Campostrini, F. Babonneau, and G. Marriotto, Structural characterization and high temperature behavior of silicon oxycarbide glasses prepared from solgel precursors contauning Si-H bonds, J. Am. Ceram. Soc. 78, 379–387 (1995).
R.J.P. Corriu, D. Leclercq, P.H. Mutin, and A. Vioux, 29Si Nuclear magnetic resonance study of the structure of silicon oxycarbide glasses derived from organosilicon precursors, J. Mater. Sci. 30, 2313–2318 (1995).
J.P. Hamilton, Sol-gel processing and characterization of borondoped silicon oxycarbide glasses, Thesis in Ceramic Science, The Pennsylvania State University, 1995.
Anant K. Singh and C.G. Pantano, Porous silicon oxycarbide glasses, J. Amer. Ceram. Soc. 79(10), 2696–2704 (1996).
C. Liu, H.Z. Chen, S. Komarneni, and C.G. Pantano, High surface area SiC/silicon oxycarbide glasses prepared from phenyltrimethoxysilane-tetramethoxysilane gels, J. Porous Materials 2, 245–252 (1996).
A.M. Wootton, M. Rappensberger, M.H. Lewis, S. Kitchin, A.P. Howes, and R. Dupree, Structural properties of multi-component silicon oxycarbide glasses derived from metal alkoxide precursors, J. Non-Cryst. Solids 204, 217–227 (1996).
R. Campostrini, G. D'Andrea, G. Carturan, R. Ceccato, and G.D. Soraru, Pyrolysis study of methyl-substituted Si-H contauning gels as precursors for oxycarbide glasses, by combined thermogravimetry, gas chromatographic and mass spectrometric analysis, J. Mater. Chem. 6(4), 585–594 (1996).
G.D. Soraru, G. D'Andrea, and A. Glisenti, XPS characterization of gel-derived silicon oxycarbide glasses, Materials Letters 27(1–5), (1996).
G.D. Soraru, E. Dallapiccola, and G. D'Andrea, Mechanical characterization of sol-gel-derived silicon oxycarbide glasses, J. Amer. Ceram. Soc. 79(8), 2074–2080 (1996).
G.D. Soraru, R. Campostrini, S. Maurina, and F. Babonneau, Gel precursor to silicon oxycarbide glasses with ultrahigh ceramic yield, J. Amer. Ceram. Soc. 80(4), 999–1004 (1997).
Anant K. Singh and C.G. Pantano, Surface chemistry and structure of silicon oxycarbide gels and glasses, J. Sol-Gel Sci. Tech. 8, 371–376 (1997).
T. Rouxel, G. Massouras, and G. Soraru, High temperature behavior of a gel-derived SiOC glass: Elasticity and viscosity, J. Sol-Gel Sci. Tech. 14, (1998).
E. Lippmaa, M. Magi, A. Samoson, G. Engelhart, and A.R. Grimmer, Structural studies of silicates by solid-state high resolution 29Si NMR, J. Am. Chem. Soc. 102, 4889–4893 (1980).
K. Moedritzer, Redistribution reactions of organometallic compounds of silicon, germanium, tin and lead, Organometallic Chemistry Review 1, 179–278 (1966).
V. Belot, R.J.P. Corriu, D. Leclercq, P.H. Mutin, and A. Vioux, Thermal redistribution reactions in crosslinked polysiloxanes, J. Polymer Sci. Chem. 30, 613–623 (1992).
P. Lespade, A. Marchand, M. Couzi, and F. Cruege, Characterization of carbonaceous materials by Raman microspectroscopy, Carbon 23(4/5), 375–385 (1984).
D. Knight and W. White, Characterization of diamond films by Raman spectroscopy, J. Mater. Res. 4(2), 385–393 (1989).
J. Biernacki and G. Wotzak, Stoichiometry of the CCSiO2 reactions, J. Amer. Ceram. Soc. 72(1), 122–129 (1989).
F.I. Hurwitz, J.Z. Gyekenyesi, P.J. Conroy, and A.L. Rivera, Nicalon/siliconoxycarbide ceramic composites, Ceram. Eng. Sci. Proc. 11(7/8), 931–946 (1990).
T. Erny, M. Seibold, O. Jarchow, and P. Greil, Microstructure development of oxycarbide composites during active-fillercontrolled polymer pyrolysis, J. Amer. Ceram. Soc. 76(1), 207–213 (1993).
P. Colombo and T.E. Paulson, Atmosphere effects in the processing of silicon carbide and silicon oxycarbide thin films and coatings, J. Sol-Gel Sci. Tech. 2, 601–604 (1994).
M. Harris, T. Chaudhary, L. Drzal, and R.M. Laune, Silicon oxycarbide coatings on graphite fibers, I. Chemistry, processing, and oxidation resistance, Mater. Sci. Eng. A A195, 223–236 (1995).
T.M. Chaudhary, H. Ho, L.T. Drzal, M. Harris, and R.M. Laune, Silicon oxycarbide coatings on graphite fibers II. Adhesion, processing and interfacial properties, Mater. Sci. Eng. A A195, 237–249 (1995).
A Donato, P. Colombo, and M.O. Abdirashid, Joining of SiC to SiC using a preceramic polymer, in High-Temperature Ceramic-Matrix Composites I: Design, Durability and Performance, edited by A.G. Evans and R. Naslaun, Ceramic Transactions Vol. 57 (The American Ceramic Society, Westerville, OH,1995), pp. 431–436.
J.C. Pivin, P. Colombo, and M. Tonidandel, Ion irradiation of preceramic polymer and thin films, J. Am. Ceram. Soc. 79, 1967–1970 (1996).
J.C. Pivin and P. Colombo, Conversion of inorganic-organic polymers to ceramics by ion implantation, Nuclear Instruments and Methods in Physics Research B, 120, 262–265 (1996).
J.C. Pivin and P. Colombo, Ceramic coatings by ion irradiation of polycarbosilanes and polysiloxanes, Part I: Conversion mechanism, J. Mater. Sci. 32, 6163–6173 (1997).
J.C. Pivin and P. Colombo, Ceramic coatings by ion irradiation of polycarbosilanes and polysiloxanes, Part II: Hardness and thermochemical stability, J. Mater. Sci. 32, 6175–6182 (1997).
E. Pippel, J. Woltersdorf, P. Colombo, and A. Donato, Structure and composition of interlayers in joints between SiC bodies, J. Europ. Ceram. Soc. 17, 1259–1265 (1997).
P. Colombo, V. Sglavo, E. Pippel, and J. Woltersdorf, Joining of reaction-bonded silicon carbide using a preceramic polymer, J. Mater. Sci. 33, 2409–2416 (1998).
P. Colombo and M. Modesti, Silicon oxycarbide foams from a silicone preceramic polymer and polyurethane, J. Sol-Gel. Sci. Tech. 14(1), 103–111 (1999).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Pantano, C.G., Singh, A.K. & Zhang, H. Silicon Oxycarbide Glasses. Journal of Sol-Gel Science and Technology 14, 7–25 (1999). https://doi.org/10.1023/A:1008765829012
Issue Date:
DOI: https://doi.org/10.1023/A:1008765829012