Thermodynamic investigation of the formation mechanism of thaumasite in cement-ground limestone cementitious materials under sulfate attack

Abstract

To provide a theoretical basis for reducing thaumasite sulfate attack (TSA) and enhancing ground limestone utilization in cement-ground limestone cementitious materials, this study examines the mechanisms underlying thaumasite formation and its relationship with temperature, cations, and ground limestone, utilizing thermodynamic principles. The findings indicate that thaumasite formation is constrained above 60.35 °C. Between 48.15 and 60.35 °C, only direct route is feasible, while below 48.15 °C, both direct and woodfordite routes occur spontaneously. As temperature decreases, Gibbs free energy changes decrease for both routes, promoting thaumasite formation. Mg²⁺ facilitates thaumasite formation via woodfordite route, while Na⁺ promotes it via direct route. With both Mg²⁺ and Na⁺ present, thaumasite formation depends on Na⁺ to Mg²⁺ ratio: below 5 favors woodfordite route, exceeding 5 favors direct route. Ground limestone reduces sulfate required for thaumasite formation, favoring the woodfordite route and exacerbating TSA; however, excessive ground limestone has a dilution effect on cement, thereby reducing thaumasite formation.

Keywords:

• Thermodynamic principles
• sulfate attack
• thaumasite
• ground limestone
• temperature
• mechanism

Disclosure statement

No potential conflict of interest was reported by the author(s).