Hostname: page-component-76fb5796d-25wd4 Total loading time: 0 Render date: 2024-04-27T08:45:39.162Z Has data issue: false hasContentIssue false
  • English
  • Français

Silicon oxycarbide glasses: Part II. Structure and properties

Published online by Cambridge University Press:  31 January 2011

Gary M. Renlund ,
Svante Prochazka  and
Robert H. Doremus
Gary M. Renlund
Affiliation:
General Electric Corporate Research, Schenectady, New York 12301
Svante Prochazka
Affiliation:
General Electric Corporate Research, Schenectady, New York 12301
Robert H. Doremus
Affiliation:
Rensselaer Polytechnic Institute, Troy, New York 12180–3590
Get access

Abstract

Silicon oxycarbide glass is formed by the pyrolysis of silicone resins and contains only silicon, oxygen, and carbon. The glass remains amorphous in x-ray diffraction to 1400 °C and shows no features in transmission electron micrographs (TEM) after heating to this temperature. After heating at higher temperature (1500–1650 °C) silicon carbide lines develop in x-ray diffraction, and fine crystalline regions of silicon carbide and graphite are found in TEM and electron diffraction. XPS shows that silicon-oxygen bonds in the glass are similar to those in amorphous and crystalline silicates; some silicons are bonded to both oxygen and carbon. Carbon is bonded to either silicon or carbon; there are no carbon-oxygen bonds in the glass. Infrared spectra are consistent with these conclusions and show silicon-oxygen and silicon-carbon vibrations, but none from carbon-oxygen bonds. 29Si-NMR shows evidence for four different bonding groups around silicon. The silicon oxycarbide structure deduced from these results is a random network of silicon-oxygen tetrahedra, with some silicons bonded to one or two carbons substituted for oxygen; these carbons are in turn tetrahedrally bonded to other silicon atoms. There are very small regions of carbon-carbon bonds only, which are not bonded in the network. This “free” carbon colors the glass black. When the glass is heated above 1400 °C this network composite rearranges in tiny regions to graphite and silicon carbide crystals. The density, coefficient of thermal expansion, hardness, elastic modulus, index of refraction, and viscosity of the silicon oxycarbide glasses are all somewhat higher than these properties in vitreous silica, probably because the silicon-carbide bonds in the network of the oxycarbide lead to a tighter, more closely packed structure. The oxycarbide glass is highly stable to temperatures up to 1600 °C and higher, because oxygen and water diffuse slowly in it.

Type
Articles
Information
Journal of Materials Research , Volume 6 , Issue 12 , December 1991 , pp. 2723 - 2734
Copyright
Copyright © Materials Research Society 1991

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

1.Renlund, G. M., Prochazka, S., and Doremus, R. H., J. Mater. Res. 6, 2716 (1991).CrossRefGoogle Scholar
2.Renlund, G. M., “Silicon Oxycarbide Glasses”, Ph.D. Thesis, Rensselaer Polytechnic Institute, Troy, NY, 1989.Google Scholar
3.Smith, C. F. and Crandall, W. B., “Method of Making Carbon Containing Glasses”, U.S. Patent No. 3 378 431 (1968).Google Scholar
4.Elmer, T. H. and Meissner, H. E., J. Am. Ceram. Soc. 59, 206 (1976).CrossRefGoogle Scholar
5.Yajima, S., Hasegawa, Y., Hayashi, J., and Iimura, M., J. Mater. Sci. 13, 2569 (1978).Google Scholar
6.Cooper, R. F. and Chyung, K., J. Mater. Sci. 22, 3148 (1987).CrossRefGoogle Scholar
7.Babonneau, F., Thorne, K., and Mackenzie, J. D., Chem. of Mater. 1, 554 (1989).CrossRefGoogle Scholar
8.Zhang, H. and Pantano, C. G., J. Am. Ceram. Soc. 73, 958 (1990).CrossRefGoogle Scholar
9.Homeny, J. and Nelson, G. G., J. Am. Ceram. Soc. 71, 386 (1988).CrossRefGoogle Scholar
10.Loehman, R. E., in Treatise on Materials Science and Technology, edited by Tomozawa, M. and Doremus, R. H. (Academic Press, San Diego, CA, 1985), Vol. 26, p. 119.Google Scholar
11.Saaka, S., Annu. Rev. Mater. Sci. 16, 29 (1986).CrossRefGoogle Scholar
12.Warren, B. E., X-Ray Diffraction (Addison-Wesley, Reading, MA, 1969), p. 253 (Dover, 1990).Google Scholar
13.Vonk, C. S., J. Appl. Cryst. 9, 433 (1976).CrossRefGoogle Scholar
14.Handbook of X-Ray Photoelectron Spectroscopy, edited by Wagner, C. D., Riggs, W. M., Davis, L. E., Moulder, J. F., and Muilenberg, G. E. (Perkin-Elmer Co., Eden Prairie, MN, 1979).Google Scholar
15.Simon, J., in Modern Aspects of the Vitreous State, edited by Mackenzie, J. D. (Butterworth's, London, 1960), Vol. I, p. 138.Google Scholar
16.Sigel, G. H., in Treatise on Materials Science and Technology, edited by Tomozawa, M. and Doremus, R. H. (Academic Press, San Diego, CA, 1975), Vol. 12, p. 1.Google Scholar
17.Sheperd, R. A. and Graham, W. R. M., “Study of the Spectra and Structure of the SiC2 Radical at 8 °K,” NBS Special Pub., 716, 604–613 (1986).Google Scholar
18.Tunistra, F. and Roenig, J. L., J. Chem. Phys. 53, 1126–1130 (1970).CrossRefGoogle Scholar
19.Nathan, M. J., Sith, J. E., and Tu, K. N., J. Appl. Phys. 45, 2370 (1974).CrossRefGoogle Scholar
20.Bansal, N. P. and Doremus, R. H., Handbook of Glass Properties (Academic Press, San Diego, CA, 1986), Chap. 2.Google Scholar
21.Urbain, G., Rev. Int. Htes. Temp, et Refr. 11, 133–145 (1974).Google Scholar
22.Wagstaff, F. E., J. Am. Ceram. Soc. 52, 650 (1969).CrossRefGoogle Scholar
23.Sosman, R. B., The Properties of Silica (Chemical Catalog Co., New York, 1927), pp. 41–59.Google Scholar
24.NMR Basic Principles and Progress edited by Diel, P., Fluck, E., and Kosfeld, R. (Springer-Verlag, Frankfurt, 1981).Google Scholar