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Two hybrid alkaline cements (HAC) based on Portland clinker, ground granulated blast furnace slag (GGBFS), fly ash and sodium sulfate, as well as an alkali-activated GGBFS/fly ash blend and a Portland cement paste were exposed to a saturated saline solution for 70 days. The combined chemical attack of chloride, magnesium and sulfate ions and the associated changes of the phase assemblage of the materials were studied by X-ray diffraction, thermal analysis and spatially resolved X-ray fluorescence spectroscopy. The experimental results revealed dissolution of ettringite, C-N-A-S-H and calcite, and the formation of gypsum, Kuzel's salt and Friedel's salt; thermodynamic modeling indicated the formation of M-S-H. The resistance of the HAC against attack by the saline solution increased with Portland clinker fraction. The capacity of portlandite to maintain pH at values above 10 is found to be a major factor controlling the resistance of HAC against corrosion in the saline solution.
Hybrid cements are composites made of Portland cement or Portland clinker and one or more supplementary cementitious materials like slag, fly ash or metakaolin, activated with an alkali salt. To date, their hydration mechanism and the phase formation at various temperatures is insufficiently understood, partly due to the large variability of the raw materials used. In the present study, three hybrid cements based on ground granulated blast furnace slag, fly ash, Portland clinker and sodium sulfate, and an alkali-activated slag/fly ash blend were cured at 10 and 21.5°C, and subsequently analyzed by XRD, 27Al MAS NMR, and TGA. The compressive strength of the hybrid cements was higher by up to 27% after 91-day curing at 10°C, compared to curing at 21.5°C. The experimental results as well as thermodynamic modeling indicate that the differences in compressive strength were related to a different phase assemblage, mainly differing amounts of strätlingite and C-N-A-S-H, and the associated differences of the volume of hydration products. While the strätlingite was amorphous to X-rays, it could be identified by 27Al MAS NMR spectroscopy, TGA and thermodynamic modeling. The microstructural properties of the hybrid cements and the alkali-activated slag/fly ash blend as well as the compatibility between thermodynamic modeling results and experimental data as a function of curing temperature and time are discussed.
Hybrid cements (cements composed of Portland clinker, supplementary cementitious materials and an alkaline activator) potentially combine advantages of conventional cements with those of alternative binders, such as low heat of hydration and improved durability in some environments. While fly ash-based hybrid cements have been studied in considerable detail, slag-dominated hybrid cements appear to have received less attention. Here, the latter materials have been studied by isothermal calorimetry, X-ray diffraction and strength testing. The heat of hydration of these cements was as low as ~50% of that of an ordinary Portland cement, while their strength after 28-day curing was in the range 31–61 MPa. The phase assemblages after 28-day curing depended on the activator, with Na2SO4 leading to ettringite and Na2CO3 leading to hemicarbonate formation, respectively, besides C–A–S–H, portlandite and hydrotalcite. The U phase was identified when a high Na2SO4 dose and/or fly ash was employed. Na2SO4 accelerated the early reaction of the Portland clinker, while Na2CO3 appeared to decrease the extent of reaction of the clinker and led to a shift of the second hydration peak (likely related to slag reaction) to later hydration times, as did substitution of slag by fly ash. Increasing Na2SO4 dose from 4 to 6% did not lead to further acceleration of hydration or improved strength.