Understanding the Relationships between Structural Features and Optical/Magnetic Properties When Designing Fe1-xMgxMoO4 as Piezochromic Compounds.
Résumé
Fe1-xMgxMoO4 compounds with x = 0, 0.25, 0.5, 0.75, and 1.0 were obtained after annealing under inert gas at T = 700 °C. All of the compounds exhibit a pressure-induced and/or temperature-induced phase transition between the two polymorphs adopted by AMoO4 compounds (A = Mn, Fe, Co, and Ni). For the FeMoO4 compound, for both the α and the β allotropic forms, the structural features have been correlated to the magnetic properties, the Mössbauer signals, and the optical absorption properties to gain a better understanding of the phenomena at the origin of the piezo(thermo)chromic behavior. The different contributions of the Mössbauer signals were attributed to the different Fe(2+) ions or Fe(3+) ions from the structural data (Wyckoff positions, bond distances and angles) and were quantified. Furthermore, the low Fe(3+) concentration (9 and 4 mol %, respectively, in the α and the β allotropic forms) was also quantified based on the magnetic susceptibility measurements. The net increase in the Fe(3+) quantity in the α-form in comparison to the β-form, which is associated with the occurrence of Fe-Mo charge transfer, is at the origin of the important divergence of coloration of the two forms. To design new piezo(thermo)chromic oxides and to control the pressure (temperature) of this first-order phase transition, FeMoO4-MgMoO4 solid solutions were synthesized. The optical contrast between the two allotropic forms was increased due to magnesium incorporation, and the phase transition (β → α) pressure increased steadily with the Mg content. A new generation of nontoxic and chemically stable piezochromic compounds that are sensible to various pressures was proposed.