Abstract
Trimethylsilylation (TMS) reactions have been carried out on acid degradable fluoro-alumino-silicate glasses containing a basic oxide. The siloxanes produced by the TMS reactions were analysed in order to gain information about the silicate structure of the glass. The results indicate a non-random arrangement of SiO4 and AlO4 tetrahedra in the glasses studied. No fluorinated derivatives of siloxanes were found, indicating that fluorine atoms are not bonded to the silicon atoms of the glass network. It is thought that fluorine atoms are instead bonded to the aluminium atoms present. The bonding of fluorine to aluminium and not to silicon atoms explains the prevention of fluorine loss as silicon tetrafluoride (SiF4) from melts containing both aluminium and a basic oxide, and in addition explains the reduction in the glass transition temperature behaviour found on incorporating fluorine into alumino-silicate glasses.
The results suggest that the environmental problem of silicon tetrafluoride loss from fluoro-silicate glass melts and its subsequent hydrolysis to hydrofluoric acid and silica can be avoided by including a basic oxide in the composition.
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References
W. A. Weyl, in "Fluorine Chemistry Vol 1" ed. J. H. Simmons (Academic Press, New York, 1950) pp. 553–574.
P. W. McMillan, "Glass-Ceramics" (Academic Press, New York, 1979).
Q. A. Juma and J. M. Parker, in "Advances in Ceramics Vol 4" ed. J. H. Simmonsq, D. R. Uhlmann and G. H. Beall (American Ceramic Society, 1982) pp. 218–323.
J. W. Flemming and D. L. Wood, Appl. Optics 22(19) (1983) 3102.
P. Dumas, J. Corset, W. Calvalho, Y. Levy and Y. Neuman, J. Non Cryst. Solids 47(2) (1982) 239.
C. Hirayama and F. E. Camp, Glass Technol 10(5) (1969) 123.
G. H. Beall, in "Advances in Nucleation and Crystallization in Glasses," ed. L. L. Hench and S. W. Frieman (American Ceramic Society, Westerville, 1971) pp. 251–260.
S. N. Hoda and G. H. Beall, in "Advances in Ceramics Vol 4" eds. J. H. Simmons, D. R. Uhlmann and G. H. Beall (American Ceramic Society, Westerville, 1982) pp. 287–300.
L. L. Hench, D. B. Spilman and J. W. Hench, "Fluoride Containing BioglassTM Compositions" US Patent 4,775,646 (1988).
W. Vogel, W. Hoeland, K. Naumann and J. Gummel, J. Non Cryst. Solids 80 (1986) 34.
R. G. Hill, M. Patel and D. Wood, "Bioceramics" Vol 4 79–86 eds. W. Bonfield, G. W. Hastings and K. E. Tanner (Butterworth Heinemann Ltd London, 1991).
R. G. Hill and A. D. Wilson, Glass Technol. 29 (1988) 150.
R. G. Hill, C. Goat and D. Wood, J. Amer. Ceram. Soc. 75 (1992) 778.
A. Dietzel, Naturwiss 29 (1941) 271.
M. J. Buerger, Am Miner. 33 (1948) 744.
D. Kumar, R. G. Ward and D. J. Williams, Discuss. Faraday Soc. 32 (1961) 147.
E. M. Rabinovich, Phys. Chem. Glasses 24 (1983) 54.
D. J. Wood and R. G. Hill, Biomaterials 12 (1991) 164.
A. D. Wilson, S. Crisp, H. J. Prosser, B. G. Lewis and S. A. Merson, Ind. Eng. Chem. Prod. Res. Dev. 19 (1980) 263.
N. H. Ray, "Developments in Ionic Polymers" Chapter 3 eds. A. D. Wilson and H. J. Prosser (Applied Science, London, 1983).
F. D. Tamas, A. K. Sakar and D. M. Roy, J. Ind. Chem. (Veszprem) 5 (1977) 115.
D. Hobbel, J. Gotz, A. Vargha and W. Wieker, J. Non Cryst. Solids 69 (1984) 145.
R. M. Smart and F. P. Glasser, J. Amer. Ceram. Soc. 57 (1974) 378.
J. Gotz, D. Hobbel and W. Weiker, J. Non Cryst. Solids 20 (1974) 378.
R. Nakamura, A. Arikata, Y. Suginohara and T. Yanagese, Kyushu Daigaku Kogaku Shuho 50(5) (1977) 635.
J. Gotz and C. R. Masson, J. Ceram Soc. A (1971) 686.
R. Atwell, B. R. Currell, C. B. Cook, H. G. Midgeley and J. R. Parsonage, ACS Coating and Plastics Div. Preprints 37(1) (1977) 67.
K. E. Kolb and K. W. Hansen, J. Amer. Ceram. Soc. 48 (1965) 439.
C. W. Lentz, J. Inorg. Chem. 3(4) (1964) 574.
H. P. Calhoun, W. D. Jamieson and C. R. Masson, J.C.S. Dalton (1979) 454.
R. G. Hill and D. Wood, J. Clinical Materials 7 (1991) 301.
F. D. Tamas, A. K. Sakar and D. M. Roy, Cem and Conc. Ass. London (1976) 55.
G. Eglinton, J. N. Firth and B. L. Welters, Chem. Geol 13 (1974) 125.
R. K. Harris, NMR of the Periodic Table.
R. K. Harris and R. H. Newman, Org. Mag. Res. 9(7) (1977) 426.
G. M. Singer and M. Tomozowa, Phys Chem. Glasses 30 (1989) 86.
W. Lowenstein, Am. Mineral. 39 (1954) 92.
S. C. Kohn, R. Dupree, M. G. Mortuza and C. M. B. Henderson, American Mineralogist 76 (1991) 309.
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Hill, R., Wood, D. & Thomas, M. Trimethylsilylation analysis of the silicate structure of fluoro-alumino-silicate glasses and the structural role of fluorine. Journal of Materials Science 34, 1767–1774 (1999). https://doi.org/10.1023/A:1004550907134
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DOI: https://doi.org/10.1023/A:1004550907134