Hostname: page-component-cd9895bd7-lnqnp Total loading time: 0 Render date: 2024-12-27T10:46:45.886Z Has data issue: false hasContentIssue false
  • English
  • Français

Titanium coordination in silicate glasses investigated using O K-edge X-ray absorption spectroscopy

Published online by Cambridge University Press:  05 July 2018

G. S. Henderson ,
Xiaoyang Liu  and
M. E. Fleet
G. S. Henderson*
Affiliation:
Department of Geology, University of Toronto, 22 Russell Street, Toronto, Ontario M5S 3B1, Canada
Xiaoyang Liu
Affiliation:
Department of Earth Sciences, University of Western Ontario, London, Ontario N6A 5B7, Canada
M. E. Fleet
Affiliation:
Department of Earth Sciences, University of Western Ontario, London, Ontario N6A 5B7, Canada
*
* E-mail: [email protected]
Get access Rights & Permissions [Opens in a new window]

Abstract

A series of titanium silicate glasses along the composition joins TiO2-SiO2, TiO2-Na2SiO3, TiO2-K2SiO3 and TiO2-CaSiO3, has been examined using oxygen K-edge X-ray absorption near edge structure spectroscopy (XANES) confined to the near-surface region. Sharp pre-edge features in the spectra can be used to determine the Ti coordination in the glasses. The presence of [4]Ti is indicated by a pre-edge peak at ∼534 eV while [5]Ti is indicated by a peak at ∼533 eV. Titanium exists in all these glasses as [4]Ti and [5]Ti with no [6]Ti being present. For alkali-containing glasses the [5]Ti site becomes more prevalent with increasing TiO2. TiO2-K2SiO3 compositions contain a greater proportion of [4]Ti than comparable Na2O compositions. This is consistent with earlier Ti L-edge findings. The TEY spectra for the TiO2-CaSiO3 compositions indicate the presence of significant amounts of [5]Ti at high TiO2 contents; however, comparison of TEY (near surface) and FY (bulk sample) XANES shows that the [5]Ti is confined to the surface of the glass sample with the bulk of the glass containing [4]Ti.

Keywords

TiXANESsilicate glasses.
Type
Research Article
Information
Mineralogical Magazine , Volume 67 , Issue 4 , August 2003 , pp. 597 - 607
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2003

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

Abbate, M., Goedkoop, J.B., de Groot, F.F.M., Grioni, M., Fuggle, J.C., Hofmann, S., Petersen, H. and Sacchi, M. (1992 Probing the depth of soft X-ray absorption spectroscopy measured in total-electronyield mode. Surface and Interface Analysis, 18, 65—69.CrossRefGoogle Scholar
Brydson, R., Williams, B.G., Engel, W., Sauer, H., Zeitler, E. and Thomas, J.M. (1987 Electron energy loss spectroscop y (EELS) and the electronic structure of titanium dioxide. Sol id Stat e Communications, 64, 609—612.CrossRefGoogle Scholar
Brydson, R., Sauer, H., Engel, W., Thomas, J.M., Zeitler, E., Kosugi, N. and Kuroda, H. (1989 Electron energy loss and X-ray absorption spectroscopy of rutile and anatase: a test of structural sensitivity. Journal of Physics of Condensed Matter, 1, 797—812.CrossRefGoogle Scholar
de Groot, F.F.M., Grioni, M., Fuggle, J.C., Ghijsen, J., Sawatzky, G.A. and Petersen, H. (1989 Oxygen 1s X-ray absorption edges of transition-metal oxides. Physical Review B, 40, 5715—5723.CrossRefGoogle ScholarPubMed
Erbil, A., Cargill III, G.S., Frahm, R. and Boehme, R.F. (1988 Total-electron-yield current measurements for near-surface extended X-ray-absorption Fine structure. Physical Review B, 37, 2450—2465.CrossRefGoogle ScholarPubMed
Farges, F. (1996 Coordination of Ti in crystalline and glassy fresnoites: A high resolution XANES spectroscopy study at the T. K-edge. Journal of Non- Crystalline Solids, 204, 53—64.CrossRefGoogle Scholar
Farges, F., Brown, G.E. and Rehr, J.J. (1996a) Coordination chemistry of Ti(IV) in silicate glasses and melts: I XAFS study of titanium coordination in oxide mo del compo unds. Geoch imic a et Cosmochimica Acta , 60, 3023—3038.CrossRefGoogle Scholar
Farges, F., Brown, G.E., Navrotsky, A., Gan, H. and Rehr, J.J. (1996b) Coordination chemistry of Ti(IV) in silicate glasses and melts: II. Glasses at ambient temperature and pressure. Geochimica et Cosmochimica Acta , 60, 3039—3053.CrossRefGoogle Scholar
Farrell, S.P. and Fleet, M.E. (2001 Sulfur K-edge XANES study of local electronic structure in ternary monosulfide solid solution [(Fe,Co,Ni)0.923S]. Physics and Chemistry of Minerals , 28, 17—27.CrossRefGoogle Scholar
Hayashi, T., Tamada, T. and Saito, H. (1983 Preparation of titania-silica glasses by the gel method. Journa l of Materials Science, 18, 3137—3142.CrossRefGoogle Scholar
Henderson, G.S. and Fleet, M.E. (1995 The structure of Ti silicate glasses by micro-Raman spectroscopy. The Canadian Mineralogist, 33, 399—408.Google Scholar
Henderson, G.S., Liu, X. and Fleet, M.E. (2002 A T. Ledge X-ray Absorption study of Ti-silicate glasses. Physics and Chemistry of Minerals, 29, 32—42.Google Scholar
Lagarde, P., Flank, A.M., Tourillon, G., Liebermann, R.C. and Itie, J.P. (1992 X-ray absorption near edge structure of quartz. Application to the structure of densified silica. Journal of Physics I France, 2, 1043—1050.CrossRefGoogle Scholar
Marcelli, A., Davolli, I., Bianconi, A., Garcia, J., Gargano, A., Natoli, C.R., Benfatto, M., Chiaradia, P., Fanfoni, M., Fritsch, E., Calas, G. and Petiau, J. (1985 Local structure in SiO2 glasses by oxygen K edge XANES. Journal de Physique , C8, 107—112.Google Scholar
Moore, P.B. and Louisnathan, S.J. (1969 The crystal structure of fresnoite, Ba2 (TiO)Si2O7. Zeitschrift für Kristallographie, 130, 438—448.CrossRefGoogle Scholar
Romano, C., Poe, B. and Henderson, G.S. (2001 Densified SiO2: A Raman and XANES oxygen Kedge spectroscopic study . Fall AGU meeting, San Francisco.Google Scholar
Ruus, R., Kikas, A., Saar, A., Ausmees, A., Nommiste, E., Aaik, J., Aidla, A., Uustare, T. and Martinson, I. (1997 Ti 2p and O 1s X-ray absorption of TiO2 polymorphs. Solid State Communications, 104, 199—203.CrossRefGoogle Scholar
Wu, Z., Paris, E., Langenhorst, F. and Seifert, F. (2002 Oxygen-metal bonding in Ti bearing compounds from O 1s spectra an. ab initio full multiplescattering calculations, Journal of Synchrotron Radiation, 9, 394—400.CrossRefGoogle Scholar