Chemical Mechanisms Involved in the Coupled Attack of Sulfate and Chloride Ions on Low-Carbon Cementitious Materials: An In-Depth Study

Abstract

This study aims to analyze the individual and combined chemical attacks of sulfate and chloride ions on cementitious materials and assess the efficiency of some selected additives (fly ash, blast furnace slag, and metakaolin) in countering this combined attack. This research is conducted in the context of construction in marine environments, where reinforced concrete structures are often subject to significant challenges due to early exposure to sulfate and chloride ions. This early exposure results in concrete expansion, cracking, and, ultimately, the corrosion of steel reinforcements. Nevertheless, the interaction between sulfate ions, chloride ions, and the cementitious matrix remains poorly understood. Previous research has drawn conflicting conclusions, with some suggesting that sulfate ions mitigate chloride attacks, while others have come to the opposite conclusion. During this study, experimental investigations were conducted by immersing powders obtained from crushed ordinary Portland cement (CEM I) paste specimens, as well as binary, ternary, and quaternary blends, in sulfate, chloride, and sulfate–chloride solutions over the course of 25 days at an early age. Results from different characterization techniques (thermogravimetric analysis, Fourier Transform Infrared spectroscopy, Raman spectroscopy, etc.) indicate that chloride ions delay the formation of ettringite, while the presence of sulfate ions accelerates the chloride attack by limiting the formation of Friedel’s salt. The Mercury Intrusion Porosimetry test confirmed these results by showing a pronounced increase in specimens’ porosity after exposure to solely sulfate after 25 days, compared to the ones exposed to both sulfate and chloride ions. Furthermore, the incorporation of multiple additives, particularly in ternary and quaternary blends, demonstrates the enhanced durability of the studied samples. This was confirmed by a Fourier Transform Infrared spectroscopy analysis, which indicated a delayed ettringite formation in these mixtures. This delay was further affirmed by the complete depletion of sulfate ions in the sulfate solutions upon contact with powders derived from the 100% CEM I paste.