Polymorphism in Bi{sub 5}Pb{sub 3}O{sub 10.5}
Journal Article
·
· Journal of Solid State Chemistry
- National Inst. for Research in Inorganic Materials, Tsukuba, Ibaraki (Japan)
- ENSCL et USTL, Villeneuve d`Ascq (France). Lab. de Cristallochimie et Physicochimie du Solide
- Univ. of Waikato, Hamilton (New Zealand). Centre for Technology
This paper describes the phase and structural relations between three polymorphs of Bi{sub 5}Pb{sub 3}O{sub 10.5}. The low-temperature stable phase named {beta}{sub L} crystallizes in the triclinic system with a = 14.903(1) {angstrom}, b = 14.184(1) {angstrom}, c = 7.2115(7) {angstrom}, {alpha} = 97.216(8){degree}, {beta} = 118.434(6){degree}, {gamma} = 80.647(8){degree}, and Z = 4. The unquenchable high-temperature stable phase labeled {beta} forms a solid solution and has an anti-{alpha}-AgI-type structure with the space group Im3m; {beta}-Bi{sub 5}Pb{sub 3}O{sub 10.5} has a = 4.40 {angstrom} at 600 C and Z = 2 (Bi{sub 5/8}Pb{sub 3/8}O{sub 10.5/8}). The metastable phase termed {beta}{sub 2} also forms a solid solution and crystallizes in the tetragonal system with the possible space group P4{sub 2}/n; {beta}{sub 2}-Bi{sub 5}Pb{sub 3}O{sub 10.5} has a = 12.132(1) {angstrom}, c = 20.059(2) {angstrom}, and Z = 9. The {beta}{sub L} phase transforms to the {beta} phase at about 585 C; on subsequent cooling, at about 560 C, the {beta} phase changes to the {beta}{sub 2} phase which is kept to room temperature. The {beta}{sub 2} phase reverts to the {beta}{sub L} phase by annealing at low temperatures, e.g., at 500 C. The structure of {beta}{sub L}-Bi{sub 5}Pb{sub 3}O{sub 10.5} is based on a pseudo-bcc {beta}-type subcell, and the transformation matrix is ({minus}2, 2, 2)/(1, {minus}1, 3)/(3/2, {1/2}, {minus}{1/2}). The structure of the {beta}{sub 2} phase is connected to that of red tetragonal PbO-type structure according to (3, 0, 0)/(0, 3, 0)/(0, 0, 4). From the viewpoint of the lone pair of electrons on Bi{sup 3+} and Pb{sup 2+}, the metastability of the {beta}{sub 2} phase is discussed.
- OSTI ID:
- 349932
- Journal Information:
- Journal of Solid State Chemistry, Journal Name: Journal of Solid State Chemistry Journal Issue: 1 Vol. 144; ISSN 0022-4596; ISSN JSSCBI
- Country of Publication:
- United States
- Language:
- English
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