The Structure of Na2O-Al2O3-SiO2 Glass: Impact on Sodium Ion Exchange in H2O and D2O
The kinetics of matrix dissolution and alkali-exchange for a series of sodium aluminosilicate glass compositions was determined at constant temperature and solution pH(D) under conditions of silica-saturation. Steady state release rate for sodium was 10 to 50 times faster than the rate of matrix dissolution, demonstrating that alkali exchange is an important long-term reaction mechanism that must be considered when modeling systems near saturation with respect to dissolved glass components. Sodium release rates were 30% slower in D2O compared to rates in H2O; but matrix dissolution rates were unaffected. These results are consistent with rupture of the O-H bond as the rate-limiting reaction in Na+-H+ exchange whereas matrix dissolution is controlled by OH- or H2O catalyzed hydrolysis of Si-O-Si and Si-O-Al bonds. Changes in Na exchange rate with increasing Al2O3 content could not be reconciled with changes in the number of non-bridging oxygen (NBO) sites in the glass alone. A simple model was used to estimate a structural energy barrier for alkali ion exchange using Na-O bond length and coordination as measured by Na K-edge XANES spectroscopy, and binding energy shifts for Si-O-Na sites measured by XPS. The energy barrier was calculated to increase from 34 kJ/mol for Na2O?2SiO2 glass to 50 kJ/mol for a glass containing 15 mol% Al2O3, consistent with stronger bonding of Na on NBO sites and increasing mechanical stiffness of the glass network with increasing Al content. The calculated ion-exchange enthalpies were then used to calculate Na ion exchange rates as a function of glass composition. Agreement between the calculated and measured Na ion exchange rates was excellent.
- Research Organization:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- AC05-76RL01830
- OSTI ID:
- 882387
- Report Number(s):
- PNNL-SA-33877; KC0303020
- Journal Information:
- Journal of Non-crystalline Solids, 296(10-26, Journal Name: Journal of Non-crystalline Solids, 296(10-26
- Country of Publication:
- United States
- Language:
- English
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