Effect of ZrSnO₄ solid solution on the crystallization behavior of Li₂O–Al₂O₃–SiO₂ glasses

Herein, the crystallization behavior of a Li₂O–Al₂O₃–SiO₂ (LAS) glass system with the addition of ZrO₂ and SnO₂ as nucleating agents was investigated using X-ray diffraction, differential scanning calorimetry, four-dimensional scanning transmission electron microscopy, and X-ray absorption fine-structure measurements. At lower heat-treatment temperatures, the addition of ZrO₂ and SnO₂ afforded a ZrSnO₄ solid solution (SS), whereas at higher heat-treatment temperatures, the ZrSnO₄ SS decomposed, affording tetragonal ZrO₂ and tetragonal SnO₂. LAS-based crystalline phases, such as β-quartz and β-spodumene phases SS, were formed after the formation of the ZrSnO₄ SS. ZrSnO₄ SS particles a few nanometers in size were present in contact with the β-quartz SS particles a few dozen nanometers in size. This suggests that the ZrSnO₄ SS served as a crystal nucleus for the β-quartz SS, promoting its growth.