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Full Record Details
Persistent URL
http://purl.org/net/epubs/work/52252
Record Status
Checked
Record Id
52252
Title
Structural variations and cation distributions in Mn
3-x
Co
x
O
4
(0 ≤ x ≤ 3) dense ceramics using neutron diffraction data
Contributors
H Bordeneuve (Paul Sabatier U.)
,
C Tenailleau (Paul Sabatier U.)
,
S Guillemet-Fritsch (Paul Sabatier U.)
,
RI Smith (STFC Rutherford Appleton Lab.)
,
E Suard (ILL)
,
A Rousset (Paul Sabatier U.)
Abstract
Single phase ceramics of cobalt manganese oxide spinels Mn3-xCoxO4 were structurally characterized by neutron powder diffraction over the whole solid solution range. For x < 1.75, ceramics obtained at room temperature by conventional sintering techniques are tetragonal, while for x >= 1.75 ceramics sintered by Spark Plasma Sintering are of cubic symmetry. The unit cells, metal?metal and metal?oxygen average bonds decrease regularly with increasing cobalt content. Rietveld refinements using neutron data show that cobalt is first preferentially substituted on the tetrahedral site for x < 1, then on the octahedral site for increasing x values. Structural methods (bond valence sum computations and calculations based on Poix?s work in oxide spinels) applied to our ceramics using element repartitions and [M?O] distances determined after neutron data refinements allowed us to specify the cation distributions in all phases. Mn2+ and/or Co2+ occupy the tetrahedral site while Mn3+, Co2+, Co(III) (cobalt in low-spin state) and Mn4+ occupy the octahedral site. The electronic conduction mechanisms in our highly densified ceramics of pure cobalt and manganese oxide spinels are explained by the hopping of polarons between adjacent Mn3+/Mn4+ and Co2+/Co(III) on the octahedral sites.
Organisation
ISIS
,
ISIS-POLARIS
,
STFC
Keywords
Materials
,
Chemistry
,
neutron diffraction
,
structure
,
cobalt manganese oxide ceramics
,
spinels
,
bond valence sum
,
cation distribution
,
electrical conduction
Funding Information
Related Research Object(s):
Licence Information:
Language
English (EN)
Type
Details
URI(s)
Local file(s)
Year
Journal Article
Solid State Sci
12, no. 3 (2010): 379-386.
doi:10.1016/j.sol…sciences.2009.11.018
2010
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