Structure of glasses and melts in the Na2O-B2O3 system from high-temperature Raman spectroscopic data: II. Superstructural units in melts

Pleiades Publishing Ltd - Tập 35 - Trang 132-140 - 2009
A. A. Osipov1, L. M. Osipova1
1Institute of Mineralogy, Ural Division, Russian Academy of Sciences, Miass, Il’men Reserve, Russia

Tóm tắt

The specific features and possible mechanisms of transformation of the intermediate-range order structure in the Na2O-B2O3 system are investigated as a function of the composition and temperature by analyzing the integrated intensities of the characteristic bands at 808, 770–780, and 750–760 cm−1 (due to the vibrations of boroxol, triborate, and di-triborate rings, respectively) in the Raman spectra of glasses and melts in this system. It is demonstrated that an increase in the Na2O concentration leads to sequential transformations of boroxol rings into triborate groups and then into di-triborate groups. An increase in the temperature results in a decrease in the fraction of main structural units joined into superstructural units. The concentration of different borate rings can change depending on the temperature due to both the more random distribution of main units in the melt structure as compared to the glass structure and the formation of nonbridging bonds within superstructural units. Moreover, different superstructural units can transform into each other.

Tài liệu tham khảo

Wright, A.C., Sinclair, R.N., Crimley, D.I., Hulme, R.A., Vedishcheva, N.M., Shakhmatkin, B.A., Hannon, A.C., Feller, S.A., Meyer, B.M., Royle, M.L., and Wilkerson, D.L., Borate Glasses, Superstructural Units and the Random Network Theory, Fiz. Khim. Stekla, 1996, vol. 22, no. 4, pp. 364–383 [Glass Phys. Chem. (Engl. transl.), 1996, vol. 22, no. 4, pp. 268–278]. Wright, A.C., Shakhmatkin, B.A., and Vedishcheva, N.M., The Chemical Structure of Oxide Glasses: A Concept Consistent with Neutron Scattering Studies?, Fiz. Khim. Stekla, 2001, vol. 27, no. 2, pp. 145–171 [Glass Phys. Chem. (Engl. transl.), 2001, vol. 27, pp. 97–113]. Brill, T.W., Raman Spectroscopy of Crystalline and Vitreous Borates, Phillips Res. Rep., 1976, no. 2, p. 117. Dwivedi, B.P. and Khanna, B.N., Cation Dependence of Raman Scattering in Alkali Borate Glasses, J. Phys. Chem. Solids, 1995, vol. 56, no. 1, pp. 39–49. Konijnendijk, W.L. and Stevels, J.M., The Structure of Borate Glasses Studied by Raman Scattering, J. Non-Cryst. Solids, 1975, vol. 18, pp. 307–331. Walrafen, G.E., Samanta, S.R., and Krishnan, P.N., Raman Investigation of Vitreous and Molten Boric Oxide, J. Chem. Phys., 1980, vol. 72, pp. 113–120. Hassan, A.K., Torell, L.M., Börjesson, L., and Doweidar, H., Structural Changes through the Liquid-Glass Transition Range: A Raman-Scattering Study, Phys. Rev. B: Condens., Matter 1992, vol. 45, no. 22, pp. 12797–12805. Tetsuji, Y., Noboru, K., Shuichi, S., and Masayuki, Y., Structural Investigation of Sodium Borate Glasses and Melts by Raman Spectroscopy: I. Quantitative Evaluation of Structural Units, J. Non-Cryst. Solids, 2003, vol. 321, pp. 137–146. Tetsuji, Y., Noboru, K., Shuichi, S., and Masayuki, Y., Structural Investigation of Sodium Borate Glasses and Melts by Raman Spectroscopy: III. Relation between the Rearrangement of Super-Structures and the Properties of Glass, J. Non-Cryst. Solids, 2003, vol. 321, pp. 157–168. Kolesova, V.A., Vibrational Spectra and the Structure of Alkali Borate Glasses, Fiz. Khim. Stekla, 1986, vol. 12, no. 1, pp. 4–13 [Sov. J. Glass Phys. Chem. (Engl. transl.), 1986, vol. 12, no. 1, pp. 1–8]. Galeener, F.L., Lucovsky, J., and Mikkelsen, J.C., Vibrational Spectra and the Structure of Pure Vitreous B2O3, Phys. Rev. B: Condens. Matter, 1980, vol. 22, no. 8, pp. 3983–3990. Galeener, F.L. and Geissberger, A.E., Raman Studies of B2O3 Structure: 10B → 11B Isotopic Substitution, J. Phys. (Paris), 1982, vol. 43, no. 12, pp. 677–682. Yiannopoulos, Y.D., Chryssikos, G.D., and Kamitsos, E.I., Structure and Properties of Alkaline Earth Borate Glasses, Phys. Chem. Glasses, 2001, vol. 42, no. 3, pp. 164–172. Chryssikos, G.D., Kamitsos, E.I., and Patsis, A.P., Effect of Li2SO4 on the Structure of Li2O-B2O3 Glasses, J. Non-Cryst. Solids, 1996, vol. 202, pp. 222–232. Akagi, R., Ohtori, N., and Umesaki, N., Raman Spectra of K2O-B2O3 Glasses and Melts, J. Non-Cryst. Solids, 1996, vol. 202, pp. 222–232. Maniu, D., Iliescu, T., Ardelean, I., Ciceo-Lucacel, R., Bolboaca, M., and Kiefer, W., Raman Study of B2O3-SrO-CuO Glasses, Vib. Spectrosc., 2002, vol. 29, pp. 241–244. Attos, O., Massot, M., Balkanski, M., and Haro-Poniatowski, E., Structure of Borovanadate Glasses Studied by Raman Spectroscopy, J. Non-Cryst. Solids, 1997, vol. 210, pp. 163–170. Maniu, D., Iliescu, T., Ardelean, I., Bratu, I., and Dem, C., Studies of Borate Vanadate Glasses Using Raman and IR Spectroscopy, Stud. Univ. Babes-Bolyai, Phys., 2001, special issue, pp. 366–371. Zhang, Z. and Soga, N., Structural Study of Densified Borate Glasses by Raman and Infrared Spectroscopy, Phys. Chem. Glasses, 1991, vol. 32, no. 4, pp. 142–148. Chryssikos, G.D., Kamitsos, E.I., Patsis, A.P., Bitsis, M.S., and Karakassides, M.S., The Devitrification of Lithium Metaborate: Polymorphism and Glass Formation, J. Non-Cryst. Solids, 1990, vol. 126, pp. 42–51. Weir, C.E. and Schroeder, R.A., Infrared Spectra of the Crystalline Inorganic Borates, J. Res. Natl. Bur. Stand., Sect. A, 1964, vol. 68, no. 5, pp. 465–487. Osipova, L.M., Osipov, A.A., and Bykov, V.N., Structure of the B2O3 Melt from Raman Spectroscopic Data, Vestn. Otd. Nauk Zemle RAN, 2003, 1(21), http://www.scgis.ru/russian/cp1251/h_dgggms/1-2003/informbul-1/magm-34.pdf. Janssen, M. and Eckert, H., 11B, 23Na Rotational Echo Double Resonance NMR: A New Approach for Studying the Spatial Cation Distribution in Sodium Borate Glasses, Solid State Ionics, 2000, vols. 136–137, pp. 1007–1014.