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In hydrating Portland cements, more than one of the AFm family of calcium aluminates may exist. Depending on the amount of carbonate and sulfate present in the cement, the most common phase to precipitate is monosulfate, monocarbonate and/or hemicarbonate. It has been reported in the literature that hemicarbonate often appears in measurements such as XRD but not predicted to form/equilibrate in thermodynamic models. With the ongoing use of commercial cements such as CEM I and CEM II containing more and more limestone, it is important to understand which hydrate solids physically precipitate and numerically predict over time. Using 27 cement samples with three w/c ratios analysed at 1, 3 and 28 days, this paper shows that although hemicarbonate was observed in a hydrating commercial Portland cement, as well as being predicted based on its carbonate (CO2/Al2O3) and sulfate (SO3/Al2O3) ratios, thermodynamic analysis did not predict it to equilibrate and form as a solid hydrate. Regardless of the w/c ratio, thermodynamic analysis did predict hemicarbonate to form for calcite contents < 2 wt.%. It appears that the dominant stability of monocarbonate in thermodynamic models leads to it precipitating and remaining as a persistent phase.
Holmes N, Russell M, Davis G, Tyrer M. Comparing the Measured and Thermodynamically Predicted AFm Phases in a Hydrating Cement. Applied Sciences. 2022; 12(19):10147. DOI: 10.3390/app121910147
This research is supported through a US-Ireland grant tri-funded by the National Science Foundation (NSF, 1805818), Science Foundation Ireland (SFI, 17/US/3424), and the Department for the Economy of Northern Ireland (DfE, USI 127).