2026-05-29T22:31:42Zhttps://riuma.uma.es/rest/oai/requestoai:riuma.uma.es:10630/383712026-02-03T10:51:24Zcom_10630_2254col_10630_37953
RIUMA. Repositorio Institucional de la Universidad de Málaga
author
Morales Sánchez, Carlos
author
Pascual, Antonio
author
Leinen, Dietmar
author
Flores, Eduardo
author
Muñoz Cortés, Esmeralda
author
Leardini, Fabrice
author
Ares Fernández, José Ramón
author
Soriano de Arpe, Leonardo
author
Jiménez Ferrer, Isabel
author
Sánchez López, Carlos
2025-04-03T12:09:32Z
2025-04-03T12:09:32Z
2022-08-03
J. Phys. Chem. C 2022, 126, 13870−13883
https://hdl.handle.net/10630/38371
10.1021/acs.jpcc.2c02060
The sulfuration of metallic iron layers into pyrite (FeS2) is preceded by an initial stage characterized by the iron transformation into monosulfide, which acts as a precursor of the disulfide. This work presents a comprehensive reaction and kinetic model of the sulfuration reaction of metallic iron thin films into monosulfides when using a molecular sulfur (S2) atmosphere. By slowing down the sulfuration reaction, we have been able to follow in-situ the evolution of the transport properties (electrical resistivity and Seebeck coefficient) of the Fe films during their sulfuration reaction to monosulfides. We show that two different stages characterize this initial sulfuration: (1) the transformation of Fe into hexagonal pyrrhotite (Fe → Fe1-xSH), and (2) a partial crystallographic transformation of this hexagonal pyrrhotite into orthorhombic pyrrhotite (Fe1-xSH → Fe1- xSO). A two-step process can explain the pyrrhotite hexagonal phase formation, being firstly controlled by the surface adsorption of S2 on the external sample interface (S2/pyrrhotite) and secondly by the diffusion of Fe atoms through the formed pyrrhotite layer. By deducing the corresponding kinetic equations in terms of the experimental parameters (S2 partial pressure and thicknesses of the layers of present species), we can explain the evolution of the electrical resistance and Seebeck coefficient of the original Fe film during its transformation into monosulfide. At the same time, the appearance of the Kirkendall effect during the monosulfide phase formation is experimental and formally justified. The comprehensive description of this first stage of the complete sulfuration process of the Fe film into pyrite provides a layout to deeply discuss the influence of these intermedium phases on the final iron disulfide film characteristics and the appearance of potential film defects related to the experimental growth conditions.
eng
Hierro - Aleaciones
Piritas
Reaction Mechanism and Kinetic Model of Fe Thin Film Transformation into Monosulfides (FeS): First Step of the Fe Films Sulfuration Process into Pyrite
journal article
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In-situ sulfuration of metallic iron _Manuscript_CMorales_REVISED.pdf
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Fe-FeS_Manuscript_Supporting Information_CMorales_REVISED.pdf