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Enhanced Sulfate Resistance: The Importance of Iron in Aluminate Hydrates

Huang, Xiao, Hu, Shuguang, Wang, Fazhou, Yang, Lu, Rao, Meijuan, Tao, Yong
ACS sustainable chemistry & engineering 2019 v.7 no.7 pp. 6792-6801
X-ray diffraction, aluminum, cement, durability, energy-dispersive X-ray analysis, iron, minerals, scanning electron microscopes, scanning electron microscopy, shrinkage, sulfates
Sulfate erosion is one of the main durability issue of ordinary Portland cement (OPC) while used in a sulfate-rich environment. Two aluminate phases in OPC, tricalcium aluminate (C₃A) and tetracalcium aluminoferrite (C₄AF), are primarily responsible for sulfate attack but with different sulfate resistant performance. This paper therefore focuses on the internal sulfate invasion to hydration products of these two aluminate minerals and attempts to explain the role of irons in hydrates. Chemical shrinkage coupled with X-ray diffraction (XRD), scanning electron microscope (SEM), and energy-dispersive X-ray spectra (EDS) are employed to determine the overall development of internal sulfate erosion of these hydrates. The results suggested that the doped iron in hydrogarnet (C₃(A,F)H₆) dramatically changes crystal growth and leads to large size of polyhedral particle to tiny cubic grain of C₃AH₆, which contributes superior performance to sulfate erosion. As to another hydrate monosulfate, the introduction of Fe in C₄(A,F)S̅H₁₂ causes a slightly worse sulfate resistance to C₄AS̅H₁₂. The substitution of iron to aluminum in hydrogarnet is the radical reason for better sulfate resistance of C₄AF to C₃A. This study greatly enhances the understanding of sulfate resistance to OPC.