Étude de la dissolution de diverses terres rares dans des liquides silicatés (CMAS) de composition variable : contribution au développement des barrières thermiques en ZRO₂-RE₂O₃ (RE=La-Lu)

Abstract : Fine particles of sand, dust or volcanic ashes ingested by aircraft engines are well-known to damage Thermal Barrier Coatings (TBC) when they infiltrate their porous microstructure as molten silicate (CMAS). They are mainly constituted of CaO-MgO-Al2O3-SiO2 in variable proportions and also contain metallic oxides. RE2Zr2O7 compositions are TBC candidate materials as they have shown efficiency to mitigate CMAS infiltration due to their reactivity with synthetic CMAS. Indeed, the dissolution reaction leads to rapid sealing of the topcoat porosity mainly due to the formation of crystalline Ca2Gd8(SiO4)6O2 apatite. However, many rare-earth silicates are likely to compete with apatite crystallization and little is known on reaction kinetics and thermodynamics involving RE2O3 and multi-component CMAS system. This work aims to determine the influence of CMAS and rare earth composition on dissolution and precipitation mechanisms. A simplified CAS was first selected with eutectic (1170°C), 65SiO2-26CaO-9Al2O3 (mol. %) composition. Dissolution of various RE2O3 with increasing basicity (RE = Yb, Dy, Gd, Sm and Nd) as well as synthetic apatite and cyclosilicate Ca3RE2(Si3O9)2 phases was then performed at 1200°C in CAS-melt. Finally, fixed MgO and Fe2O3 contents were added to CAS melt with an increasing CaO/SiO2 ratio. The results showed that RE2O3 dissolution mechanism is indirect. Apatite formation results from local equilibrium at the interface with solid RE2O3 whatever the rare earth and CMAS composition. Its crystallization is favored when Ca2+ and RE3+ ionic radii are close as they are both distributed within 9-fold coordination sites. Conversely, Ca and RE mismatch leads to rapid nucleation of cyclosilicate phase in CAS as they are preferentially distributed within a 6-fold coordination site. MgO and Fe2O3 addition in CAS as well as RE2O3 basicity tend to increase RE solubility in silicate melt. Phases in thermodynamic equilibrium strongly depend on CMAS composition but generally exhibits lower RE solubility and dissolution rate in melt than apatite
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François Perrudin. Étude de la dissolution de diverses terres rares dans des liquides silicatés (CMAS) de composition variable : contribution au développement des barrières thermiques en ZRO₂-RE₂O₃ (RE=La-Lu). Chimie. Université de Lorraine, 2018. Français. ⟨NNT : 2018LORR0277⟩. ⟨tel-02104530⟩

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