Phase Stability and Structural Reorganization of Silica in Cherts Under Thermal and Mechanochemical Stress.

This work investigated the structural response and phase transformation dynamics of silica-bearing cherts subjected to high-temperature processing (up to 1400 °C) and prolonged mechanochemical activation. Through a combination of X-ray diffraction (XRD) with Rietveld refinement, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and transmission electron microscopy (HRTEM), we trace the crystallographic pathways of quartz, moganite, tridymite, and cristobalite under controlled thermal and mechanical stress regimes. The experimental results demonstrated that phase behavior is highly dependent on intrinsic properties such as initial phase composition, impurity presence, and crystallinity. Heating at 1400 °C induced irreversible conversion of quartz, moganite, and tridymite into cristobalite. Samples enriched in cristobalite and tridymite exhibited notable increases in crystallinity, whereas quartz-dominant samples showed either stability or a decline in structural order. Rietveld analyses underscored the critical influence of microstrain and crystallite size on thermal resilience and phase persistence. Thermal profiles revealed by DSC and TGA expose overlapping processes including polymorphic transitions, minor phase dehydration, and redox-driven changes, likely associated with trace components. Mechanochemical processing resulted in partial amorphization and the emergence of phases such as opal and feldspar minerals (microcline, albite, anorthite), interpreted as the product of lattice collapse and subsequent reprecipitation. Heat treatment of chert leads to a progressive rearrangement and recrystallization of its silica phases: quartz collapses around 1000 °C before recovering, tridymite emerges as an intermediate phase, and cristobalite shows the greatest crystallite size growth and least deformation at 1400 °C. These phase changes serve as markers of high-temperature exposure, guiding the identification of heat-altered lithic artefacts, reconstructing geological and diagenetic histories, and allowing engineers to adjust the thermal expansion of ceramic materials. Mechanochemical results provide new insights into the physicochemical evolution of metastable silica systems and offer valuable implications for the design and thermal conditioning of silica-based functional materials used in high-temperature ceramics, glasses, and refractory applications. From a geoarchaeological standpoint, the mechanochemically treated material could simulate natural weathering of prehistoric chert tools, providing insights into diagenetic pathways and lithic degradation processes.