Transformations induced by hydrostatic pressure on lead metasilicate phases

Abstract

For most silicates, controlling the crystallization - through the nucleation, growth, and stabilization of distinct crystalline phase - is critical to achieving the desired physical properties in the final glass-ceramic product. In this context, lead metasilicate PbSiO3 (PS) represents an ideal model system for investigating structural evolution under varying pressure and temperature conditions. This is primarily due to its distinct Raman signatures and the capability of resolving its structure with high precision through diffraction measurements. These attributes enable a comprehensive evaluation of the thermodynamic quantities involved in this complex process, which are essential for the physical description of the crystallization of glasses undergoing heterogeneous nucleation. We report on high-pressure in situ analyses of three crystalline phases of PS: a stable monoclinic structure, a metastable hexagonal structure, and a lower symmetry metastable phase. Combined high-pressure Raman and synchrotron X-ray diffraction indicate that the structures are highly sensitive to the application of hydrostatic pressure and that significant structural rearrangements can be achieved in moderate pressure regimes. Such analyses also enabled determining important thermodynamic variables of those systems, such as compressibility. From an applied perspective, our findings demonstrate that the application of pressure achievable using large-volume presses and capable of altering the energy states of such phases, can be regarded as a promising strategy to influence the stages of the overall crystallization process. This approach opens new avenues for the development of novel structures and properties in the resulting glass-ceramic materials