Modeling the Onset of Phase Separation in CaO-SiO₂-CaCl₂ Chlorine-Containing Silicate Glasses

The addition of chlorine into a bioactive glass composition is expected to reduce its abrasiveness and increase its bioactivity, which is important for dental applications such as toothpastes. There is a lack of information and understanding regarding the structural role of chlorine in chlorine-containing bioactive silicate glasses. This has prompted classical core-shell model molecular dynamics simulations of (50 - x/2)CaO-(50 - x/2)SiO₂-xCaCl₂ glasses to be performed, where x ranges from x = 0.0 to 43.1 mol % CaCl₂. These ternary glasses are advantageous for a fundamental study because they do not have additional network formers (e.g., phosphorus pentoxide) or modifiers (e.g., sodium) typically found in bioactive glass compositions. The (50 - x/2)CaO-(50 - x/2)SiO₂-xCaCl₂ glasses were seen to become phase-separated around the x = 16.1 mol % CaCl₂ composition, and chlorine predominantly coordinated with calcium. These findings provide a solid foundation for further computational modeling work on more complex chlorine-containing bioactive glass compositions.