Glass Durability Modeling, Activated Complex Theory (ACT)
The most important requirement for high-level waste glass acceptance for disposal in a geological repository is the chemical durability, expressed as a glass dissolution rate. During the early stages of glass dissolution in near static conditions that represent a repository disposal environment, a gel layer resembling a membrane forms on the glass surface through which ions exchange between the glass and the leachant. The hydrated gel layer exhibits acid/base properties which are manifested as the pH dependence of the thickness and nature of the gel layer. The gel layer has been found to age into either clay mineral assemblages or zeolite mineral assemblages. The formation of one phase preferentially over the other has been experimentally related to changes in the pH of the leachant and related to the relative amounts of Al{sup +3} and Fe{sup +3} in a glass. The formation of clay mineral assemblages on the leached glass surface layers ,lower pH and Fe{sup +3} rich glasses, causes the dissolution rate to slow to a long-term steady state rate. The formation of zeolite mineral assemblages ,higher pH and Al{sup +3} rich glasses, on leached glass surface layers causes the dissolution rate to increase and return to the initial high forward rate. The return to the forward dissolution rate is undesirable for long-term performance of glass in a disposal environment. An investigation into the role of glass stoichiometry, in terms of the quasi-crystalline mineral species in a glass, has shown that the chemistry and structure in the parent glass appear to control the activated surface complexes that form in the leached layers, and these mineral complexes ,some Fe{sup +3} rich and some Al{sup +3} rich, play a role in whether or not clays or zeolites are the dominant species formed on the leached glass surface. The chemistry and structure, in terms of Q distributions of the parent glass, are well represented by the atomic ratios of the glass forming components. Thus, glass dissolution modeling using simple atomic ratios is shown to represent the structural effects of the glass on the dissolution and the formation of activated complexes in the glass leached layer. This provides two different methods by which a linear glass durability model can be formulated. One based on the quasi- crystalline mineral species in a glass and one based on cation ratios in the glass: both are related to the activated complexes on the surface by the law of mass action. The former would allow a new Thermodynamic Hydration Energy Model to be developed based on the hydration of the quasi-crystalline mineral species if all the pertinent thermodynamic data were available. Since the pertinent thermodynamic data is not available, the quasi-crystalline mineral species and the activated complexes can be related to cation ratios in the glass by the law of mass action. The cation ratio model can, thus, be used by waste form producers to formulate durable glasses based on fundamental structural and activated complex theories. Moreover, glass durability model based on atomic ratios simplifies HLW glass process control in that the measured ratios of only a few waste components and glass formers can be used to predict complex HLW glass performance with a high degree of accuracy, e.g. an R{sup 2} approximately 0.97.
- Research Organization:
- Savannah River Site (SRS), Aiken, SC (United States)
- Sponsoring Organization:
- US Department of Energy (US)
- DOE Contract Number:
- AC09-96SR18500
- OSTI ID:
- 838909
- Report Number(s):
- WSRC-MS-2004-00663, Rev. 0; JNUMAM; TRN: US0501552
- Journal Information:
- Journal of Nuclear Materials, Other Information: PBD: 4 Feb 2005; ISSN 0022-3115
- Country of Publication:
- United States
- Language:
- English
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