Westfälische Wilhelms-Universität
Münster
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Sonderforschungsbereich 458 Ionenbewegung in Materialien mit ungeordneten Strukturen - vom Elementarschritt zum makroskopischen Transport - Schlossplatz 4/7 48149 Münster Sprecher: Prof. Dr. Klaus Funke |
Tel. (0251) 83-23402
Fax: (0251) 83-23403 e-mail: sfb458gs@uni-muenster.de www: http://www.uni-muenster.de/Chemie/PC/sfb |
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Forschungsschwerpunkte 2001 - 2002 Sonderforschungsbereiche
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Mixed cation effects in alkali alkaline-earth silicate glasses
Compared to the
investigations conducted on mixed-alkali glasses which until today stimulate the discussion about the
underlying microscopic jump mechanisms, little is known about the mobility of alkaline-earthions in silicate
glasses. This is surprising since many silicate glasses used for technical applications, such as the float glass
produced by Pilkington plc. with 72 mol% SiO2, 13 mol% Na2O,
9 mol% CaO, and 4 mol% MgO, contain alkali and alkaline-earth oxides.Diffusion of the
radioactive isotopes 45Ca and 133Ba in alkali alkaline-earth silicate glasses of
compositions A2O-2CaO-4SiO2 with A=Li, K, Cs and
K2O-2BaO-4SiO2 was investigated at temperatures below the respective
glass-transition temperatures. The diffusion profiles of the radiotracers were recorded by means of an ion-beam
sputtering technique in conjunction with activity measurements. Analysis of the calcium and barium profiles is
based on the thin-film solution of the diffusion equation and a contribution which reflects the instrumental
broadening of the profiles caused by sputtering effects. The diffusion coefficients of the alkaline-earth ions
were determined down to values of as low as 10-21m2s-1. Our
diffusion data enables us to determine accurate values for the activation enthalpy of diffusion and the
pre-exponential factor. The activation enthalpies reveal a distinct correlation with the radius ratio of the
alkaline-earth ions to the alkali ions and show that the alkaline-earth ions are most mobile when the radii of the
alkaline-earth and alkali ionsare similar. The diffusion study strongly supports recent results from mechanical
loss spectroscopy. A model is proposed which qualitatively explains the correlation of the alkaline-earth
mobility with the radius ratio of the cations.
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