A Study of Na 2 O-TiO 2 -SiO 2 Glasses by Infrared Spectroscopy

Abstract

The infrared absorption spectra of six Na₂O-TiO₂-SiO₂ glasses in the frequency range of 1600 to 200 cm⁻¹ are reported. These glasses, having a SiO₂/Na₂O molar ratio of 1.07 to 3.54, and containing 20 or 25 mole % TiO₂, demonstrate two main absorptions at ∼950 cm⁻¹ and at ∼450 cm⁻¹. A weak absorption at ∼790 cm⁻¹ becomes progressively weaker in intensity, and a weak shoulder at 1050 cm⁻¹ appears with increasing Na₂O content. The frequency of the absorption band at ∼950 cm⁻¹ is found to decrease markedly and systematically with a decrease in the SiO₂/Na₂O molar ratio, whereas the frequency of the band at ∼450cm⁻¹ shows a slight increase. The infrared results may be interpreted in terms of a lowering of symmetry occurring for the SiO₄ units. The effect of TiO₂ content on the relationship between vibrational frequency is discussed. The frequency composition curves for glasses containing 20 and 25 mole % of TiO₂ intersect at SiO₂/Na₂O ratio ∼2. A reversal in the frequency vs SiO₂/Na₂O ratio relation was also found at SiO₂/Na₂O ∼2 for the sodium silicate glasses.

Keywords

Infrared spectroscopy Compositional effects

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References

Hamilton

E. H.

and Cleek

G. W.

, J. Res. Nat. Bur. Stand. 61, No. 2, 89 (1958).

Bayer

and Hoffmann

, Glass Technol. 7, No. 3, 94 (1966).

Turnbull

R. C.

and Lawrence

W. C.

, J. Am. Ceram. Soc. 35, No. 2, 48 (1952).

Beals

M. D.

and Strimple

J. H.

, Glass Ind. 44, 679 (1963).

Hirayama

and Berg

, Phys. Chem. Glasses 2, No. 5, 145 (1961).

Manghnani

M. H.

, J. Am. Ceram. Soc. 55, 360 (1972).

Charles

R. J.

, in Progress in Ceramic Science, Burke

J. E.

, Ed. (Pergamon Press, Elmsford, N. Y., 1961), Vol. 1, p. 1.

Shaw

R. R.

and Uhlmann

D. R.

, J. Non-Crystalline Solids 5, 237 (1971).

Manghnani

M. H.

, to be submitted.

10.

Ferraro

J. R.

, Low Frequency Vibrations of Inorganic and Coordination Compounds (Plenum Press, New York, 1971).

11.

Gonzalez-Vilchez

and Griffiths

W. P.

, J. Chem. Soc. Dalton 1416 (1972).

12.

Lippincott

E. R.

Van Valkenburg

Weir

C. E.

, and Bunting

E. N.

, J. Res. Nat. Bur. Stand. 61, 61 (1958).

13.

Ferraro

J. R.

Manghnani

M. H.

, and Quattrochi

, Phys. Chem. Glasses 13, 116 (1972).

14.

Ferraro

J. R.

and Manghnani

M. H.

, J. Appl. Phys. 43, 4395 (1972).

15.

Ferraro

J. R.

Basile

L. J.

, and Manghnani

M. H.

, J. Appl. Phys. submitted for publication.

16.

Trap

H. J. L.

and Stevels

J. M.

, Phys. Chem. Glasses 1, No. 4, 107 (1968).

17.

One of the referees of this paper commented on the recent Raman study [see Tobin

M. C.

and Baak

, J. Opt. Soc. Am. 58, 1459 (1968)], in which a related glass containing 10% titanium exhibited vibrations assigned to TiO motions. The reasons for the differences are not immediately apparent, but our glasses contain more Na₂O, and vibrations due to the latter effects could obscure any TiO vibrations.