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Reactivity of Silicates 1. Kinetic Studies of the Hydrolysis of Linear and Cyclic Siloxanes as Models for Defect Structure in Silicates

Published online by Cambridge University Press:  28 February 2011

Carol A. Balfe ,
Kenneth J. Ward ,
David R. Tallant  and
Sheryl L. Martinez
Carol A. Balfe
Affiliation:
Sandia National Laboratories, Albuquerque, NM 87185
Kenneth J. Ward
Affiliation:
Sandia National Laboratories, Albuquerque, NM 87185
David R. Tallant
Affiliation:
Sandia National Laboratories, Albuquerque, NM 87185
Sheryl L. Martinez
Affiliation:
Sandia National Laboratories, Albuquerque, NM 87185
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Abstract

The kinetics of hydrolysis of hexamethylcyclotrisiloxane and di-t-butyldimesitylcyclodisiloxane in tetrahydrofuran solution have been determined and compared to hydrolysis rates of silica defects. In the presence of sufficient excess witer, the first-order rate constant of the cyclotrisiloxine, k= 3.8 × 10−3 min is similar to the rate constant, k = 5.2 × 10−1 min, of the disappearance of the D2 Raman silica defect band it has been proposed to model. Limited hydrolysis rate data for the cyclodisiloxane suggests that it hydrolyzes at least four times faster than does the cyclotrisiloxane. These data are consistent with rate data available for silica crack growth and support the assignment of highly strained siloxane bonds at the crack tip to cyclodisiloxanes. Infrared spectra determined for the cyclodisiloxanes lend further support to this model.

Type
Articles
Information
MRS Online Proceedings Library (OPL) , Volume 73: Symposium H – Better Ceramics Through Chemistry II , 1986 , 619
Copyright
Copyright © Materials Research Society 1986

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References

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