Fluoride-containing alkali-free setting accelerators are a common type of admixture used in tunnel shotcrete but few studies in the literature focus on the effect of their fluoride compounds on the setting and hardening properties of accelerated cement paste under low environment temperatures. Tunnel shotcrete in cold regions or winter construction periods would be obviously influenced by low environment temperatures, especially for its fast setting and quick support applications. The objective of this work is to evaluate the early age hydration behavior of different accelerated cement pastes under 20 °C and 5 °C environment temperatures. In this study, setting time measurement, early age strength development, hydration ion leaching concentration, isothermal calorimetry, X-ray diffraction, and ESEM were performed on cement systems prepared with a non-fluoride alkali-free accelerator (aluminum sulfate solution with over 60% solid content) and a designed fluoride-containing alkali-free setting accelerator (aluminum sulfate and fluoride compound). The results showed that the fluorides obtained in alkali-free accelerators promote C3S dissolution and massive ettringite needles together with monosulfoaluminate (AFm) hydrate formation, thus leading to a quicker setting effect and low sensitivity to low environment temperatures than in non- fluoride groups. However, the rate of mechanical strength development of cement pastes hydrated within 24 h was decreased obviously when fluorine-containing alkali-free accelerator was used. This phenomenon is mainly related to the crystallization of thin-plate shape calcium fluoride (CaF2) formations and promoted conversion of ettringite to monosulfoaluminate hydrate in the accelerating period, thus weakening the denseness of C-S-H gel and inhibiting alite further hydration.
Keywords: alkali-free accelerator; calcium fluoride; early age hydration; ettringite.