Cation diffusion patterns across the magneto-structural transition in Fe7S8
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Date
2019-06-28
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Journal Article
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Abstract
Migration of atoms in solids during diffusion-dependent reactions is relatively fast and generally not directly recordable in experiments. Here we present an experimental framework that includes fast differential scanning calorimetry to resolve cation-migration paths in crystalline solids using the reversible magneto-structural transition of 4C to 1C pyrrhotite as a testbed. The transition between these two polymorphic Fe7S8 phases at about 600 K is a diffusive process of vacancies, respectively of Fe in octahedral interstitial sites within a hexagonal close-packed lattice of sulfur, and it coincides with the Curie temperature of 4C pyrrhotite. The Fe cations migrate along three kinds of diffusion paths, and their enthalpy contributions to the total reaction enthalpy are taken to define the diffusion patterns in the endothermic reaction and the exothermic back-reaction, respectively. Our experimental findings provide insight into the potential of diffusion patterns to disentangle ordering mechanisms in solids.
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published
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21 (24)
Pages / Article No.
13040 - 13046
Publisher
Royal Society of Chemistry
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03661 - Löffler, Jörg F. / Löffler, Jörg F.
03734 - Jackson, Andrew / Jackson, Andrew
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Funding
153173 - Magnetic thermodynamics of non-stoichiometric Fe-based mineral phases (SNF)