Phase, structure, and hygroscopic property evolutions of alkali-silica reaction gels under freeze drying

Abstract

Alkali-silica reaction (ASR), a detrimental process causing volume expansion and cracking in concrete by forming hygroscopic and swellable gel-like products, has been a long-standing challenge faced by concrete structures across the world. Understanding the underlying mechanisms of formation, moisture uptake and swelling of ASR gels requires thorough characterizations, where an appropriate drying method to remove free water and stop the reactions in the samples is essential. This study aims to elucidate the effect of freeze-drying, an emerging drying technique increasingly employed in sample preparations, on the phase, molecular structure, and moisture absorption behavior of ASR gels. Towards this end, six ASR gels with three calcium-to-silica (Ca/Si) ratios (0.1, 0.3, and 0.5) and two alkali-to-silica [(Na + K)/Si] ratios of 0.3 (low-alkali gels) and 1.0 (high-alkali gels) were studied. The results indicate that the chemical bonds and mineral components of ASR gels can be maintained during the removal of free and loosely bound water in freeze drying, while slight changes in crystallization and relative contents of alkali-silicate hydrate and calcium silicate hydrate phases were observed, in particular, for the high-alkali ASR gels. Although slight decreases in Q¹, Q^2, and Q³ silica polymerization sites and increases in the mean chain length and degree of polymerization were observed from the nuclear magnetic resonance (NMR) spectroscopy, the intrinsic layered silicate structure of ASR gels remains. The moisture absorption of low-alkali and high-alkali ASR gels was found to be governed by gel pores and mesopores, respectively. After freeze-drying, slight increases in moisture sorption (a 6.8 % increase in absorption and a 2.2 % decrease in desorption) and enhanced hysteresis were observed from the low-alkali gels. The high-alkali gels, however, showed a slight decrease in hygroscopicity along with a 16.6 % reduction of mesopores.