Calcium-lead fluoro-vanadinite apatites. I. Disequilibrium structures
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Published on: June 8, 2016
1Centre for Advanced Research of Ecomaterials, Institute of Environmental Science and Engineering, Innovation Centre, Nanyang Technological University, Block 2, Unit 237, 18 Nanyang Drive, Singapore 637723, Singapore. zldong@ntu.edu.sg
Abstract:
The synthetic vanadinites (Pb(x)Ca(10-x))(VO4)6F2delta, 1 < x < 9, adopt a P6(3)/m apatite structure with 9.7590 (1) < or = a < or = 10.1179 (1) A and 7.0434 (3) < or = c < or = 7.4021 (1) A. The partitioning of calcium and lead over the AI(4f) and AII(6h) positions is nonstoichiometric with lead preferentially entering the larger AII site. High-resolution electron microscopy showed that samples annealed for 10 h at 1073 K are in disequilibrium with calcium- and lead-rich microdomains co-existing at unit-cell scales. For (Pb5Ca5)(VO4)6F2delta, sintering in excess of 2 weeks is required for the metals to order macroscopically. As annealing progresses, c/a, the partitioning coefficient kPb(AI/AII) and the AIO6 metaprism twist angle (phi) adjust cooperatively to enlarge the apatite channel, and thereby accommodate higher lead content. These results demonstrate that phi is a sensitive measure of disequilibrium and a useful device for monitoring changes in apatite topology as a function of composition.
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