Intergrowth Structure in U- and Hf-Bearing Pyrochlore and Zirconolite: TEM Investigation
Transmission electron microscopy results from a sintered ceramics with stoichiometry of Ca(U{sub 0.5}Ce{sub 0.25}Hf{sub 0.25})Ti{sub 2}O{sub 7} show the material contains both pyrochlore and zirconolite phases and structural intergrowth of zirconolite lamellae within pyrochlore. (001) plane of zirconolite is parallel to (111) plane of pyrochlore because of their structural similarities. The pyrochlore is relatively rich in U, Ce, and Ca with respect to the coexisting zirconolite. Average compositions for the coexisting pyrochlore and zirconolite produced by sintering at 1350 C are (Ca{sub 1.01}Ce{sub 0.13}{sup 3+}Ce{sub 0.19}{sup 4+}U{sub 0.52}Hf{sub 0.18})(Ti{sub 1.95}Hf{sub 0.05})O{sub 7} (with U/(U+Hf) (in the AB sites) = 0.74) and (Ca{sub 0.91}Ce{sub 0.09})(Ce{sub 0.08}{sup 3+}U{sub 0.26}Hf{sub 0.66}Ti{sub 0.01})Ti{sub 2.00}O{sub 7} (with U/(U+Hf) = 0.28) respectively. A single pyrochlore ((Ca,U,Hf){sub 2}Ti{sub 2}O{sub 7}) phase may be synthesized at 1350 C if the ratio of U/(U+Hf) is greater than 0.72, and a single zirconolite (Ca(Hf,U)Ti{sub 2}O{sub 7}) phase may be synthesized at 1350 C if the ratio of U/(U+Hf) is less than 0.28. An amorphous leached layer that is rich in Ti and Hf forms on the surface after the ceramics has been leached in pH 4 buffered solution. The thickness of the layer ranges from 5 nm to 15 nm. It is suggested that under these conditions, the leached layer functions as a protective layer, and reduces the leaching rate over time.
- Research Organization:
- Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
- Sponsoring Organization:
- US Department of Energy (US)
- DOE Contract Number:
- W-7405-ENG-48
- OSTI ID:
- 15006446
- Report Number(s):
- UCRL-JC-151293; TRN: US200411%%84
- Resource Relation:
- Conference: Materials Research Society Fall Meeting, Boston, MA (US), 12/02/2002--12/06/2002; Other Information: PBD: 4 Dec 2002
- Country of Publication:
- United States
- Language:
- English
Similar Records
Saturation of impurity-rich phases in a cerium-substituted pyrochlore-rich titanate ceramic: part 1 experimental results
Preparation and characterization of {sup 238}Pu-ceramics for radiation damage experiments