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Title: Solid solution limits in SYNROC zirconolite

Journal Article · · Nucl. Chem. Waste Manage.; (United States)
OSTI ID:6386797

In the titanate ceramic high-level wasteform SYNROC, zirconolite (CaZrTi/sub 2/O/sub 7/) is the primary host for uranium and tetravalent actinides, and the secondary host for rare earths and trivalent actinides. Significant amounts of other fission products and processing contaminants also enter into solid solution in its lattice. Experiments investigating the binary joins between CaZrTi/sub 2/O/sub 7/ and various real or hypothetical end-members show that zirconolite solid solutions can accept 27 wt% UO/sub 2/, 20% ThO/sub 2/, at least 29% rare earth oxides, 14% Nb/sub 2/O/sub 3/, 7% Al/sub 2/O/sub 3/, 4% MgO, 4% FeO or 5% MnO, but only limited amounts of Na/sub 2/O, SrO and NiO. The smaller cations Nb/sup 5 +/, Al/sup 3 +/, Mg/sup 2 +/ and Fe/sup 2 +/ are partitioned into the Ti-sites. Rare earths are preferentially accommodated in the Ca-site but also occupy the Zr-site. Th/sup 4 +/ and Mn/sup 2 +/ are strongly partitioned into the Ca-site. In contrast with natural zirconolites, U/sup 4 +/ enters the Zr-site, but can be accommodated in both Ca- and Zrsites via coupled substitution of a small lower valence cation e.g., Mg/sup 2 +/, Fe/sup 2 +/, Fe/sup 3 +/, or Al/sup 3 +/ for Ti/sup 4 +/. A comparison of natural and synthetic zirconolites indicates that the structure requires at least 50 mole % occupancy of the Ti-sites by Ti/sup 4 +/ and 70 mole % occupancy of the Zr-site by Zr/sup 4 +/.

Research Organization:
Research School of Earth Sciences, Australian National University, Canberra, ACT
OSTI ID:
6386797
Journal Information:
Nucl. Chem. Waste Manage.; (United States), Vol. 4:3
Country of Publication:
United States
Language:
English