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Effect of Gallium Oxide on Phase Assemblage in Apatite and Whitlockite Hosts for Waste Immobilization

Published online by Cambridge University Press:  01 February 2011

Lee. A. Gerrard
Affiliation:
Materials Science Research Division, AWE, Aldermaston, Berkshire, UK
Shirley. K. Fong
Affiliation:
Materials Science Research Division, AWE, Aldermaston, Berkshire, UK
Brian. L. Metcalfe
Affiliation:
Materials Science Research Division, AWE, Aldermaston, Berkshire, UK
Ian. W. Donald
Affiliation:
Materials Science Research Division, AWE, Aldermaston, Berkshire, UK
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Abstract

To immobilize halide and actinide ions present in specific ILW waste a process has been developed that uses mineral phases as the host material. The mechanism of substitution of gallium into these phases will have a large effect on the phase assemblage. This will inevitably affect the total amount of halide that can be immobilized in to total phase mixture.

The full simulated waste stream composition containing varying concentrations (1–40 wt.%) of gallium oxide was studied. Also nominal compositions for gallium doped fluorapatites (Ca10-1.5xGax)F2(PO4)6 (x = 0, 0.25, 0.5, 0.75, 1.0) and gallium doped whitlockites Ca9Gay(PO4)6+y (x = 0.2, 0.4, 0.6, 0.8, 1.0) were prepared at 750–1050 °C.

These were studied by powder x-ray diffraction (XRD) to determine the phase assemblage and solid solution limits of gallium in the apatite and whitlockite phases. It was found that a complete solid solution was formed between whitlockite, Ca3(PO4)2, and Ca9Gay(PO4)6+y. In the nominal apatite compositions it was found that gallium did not substitute into the apatite structure but was instead partitioned over Ca9Gay(PO4)6+y, gallium phosphate, and unreacted gallium oxide. At higher temperatures gallium suppressed the formation of the apatite phase and was largely partitioned into the Ca9Gay(PO4)6+y phase whereas at lower temperature the majority was present as unreacted Ga2O3. In the full DCHP compositions it was found that gallium is likely to be partitioned over a number of phases including apatite, cationdoped whitlockite and gallium phosphate.

Type
Research Article
Copyright
Copyright © Materials Research Society 2008

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