From Molten Calcium Aluminates through Phase Transitions to Cement Phases

Abstract Crystalline calcium aluminates are a critical setting agent in cement. To date, few have explored the microscopic and dynamic mechanism of the transitions from molten aluminate liquids, through the supercooled state to glassy and crystalline phases, during cement clinker production. Herein, the first in situ measurements of viscosity and density are reported across all the principal molten phases, relevant to their eventual crystalline structures. Bulk atomistic computer simulations confirm that thermophysical properties scale with the evolution of network substructures interpenetrating melts on the nanoscale. It is demonstrated that the glass transition temperature (Tg) follows the eutectic profile of the liquidus temperature (Tm), coinciding with the melting zone in cement production. The viscosity has been uniquely charted over 14 decades for each calcium‐aluminate phase, projecting and justifying the different temperature zones used in cement manufacture. The fragile–strong phase transitions are revealed across all supercooled phases coinciding with heterogeneous nucleation close to 1.2Tg, where sintering and quenching occur in industrial‐scale cement processing.