Local Structural Changes in High-Alumina, Low-Lithium Glass-Ceramics During Crystallization.

Abstract

In this study, we investigate the phase transition process during high-alumina, low-lithium glass-ceramics (ZnO-MgO-Li₂O-SiO₂-Al₂O₃) crystallization. The differential scanning calorimetry and high-temperature X-ray diffraction results show that approximately 10 wt.% of (Zn, Mg)Al₂O₄ crystals precipitated when the heat treatment temperature reached 850 °C, indicating that a large number of nuclei had already formed during the earlier stages of heat treatment. Field emission transmission electron microscopy used to observe the microstructure of glass-ceramics after staged heat treatment revealed that cation migration occurred during the nucleation process. Zn and Mg aggregated around Al to form (Zn, Mg)Al₂O₄ nuclei, which provided sites for crystal growth. Moreover, high-valence Zr aggregated outside the glass network, leading to the formation of nanocrystals. Raman spectroscopy analysis of samples at different stages of crystallization revealed that during spinel precipitation, the Q³ and Q⁴ structural units in the glass network increased significantly, along with an increase in the number of bridging oxygens. Highly coordinated Al originally present in the network mainly participated in spinel nucleation, effectively suppressing the subsequent formation of Li_xAl_xSi_1-xO₂, which eventually resulted in the successful preparation of glass-ceramics with (Zn, Mg)Al₂O₄ and ZrO₂ as the main crystalline phases. The grains in this glass-ceramic are all nanocrystals. Its Vickers hardness and flexural strength can reach up to 875 Hv and 350 MPa, respectively, while the visible light transmittance of the glass-ceramic reaches 81.5%. This material shows potential for applications in touchscreen protection, aircraft and high-speed train windshields, and related fields.