This study investigated the influence of different cooling regimes on the microstructure and consequent reactivity of belite-sulfoaluminate clinkers. The cement clinkers were synthesized by incorporating secondary raw materials, such as titanogypsum and bottom ash, to the natural raw materials. Clinker phases were determined by Rietveld quantitative phase analysis, while the distribution morphology and the incorporation of substitute ions in the phases were characterized by scanning electron microscopy using energy-dispersive X-ray spectroscopy (SEM/EDS). Clinker reactivity was studied using isothermal calorimetry and was additionally investigated through compressive strength, which was determined for the cement prepared from the synthesized clinkers. X-ray diffraction analysis showed that, as well as the three main phases (belite, calcium sulfoaluminate, and ferrite), the clinkers contained additional minor phases (mayenite, gehlenite, arkanite, periclase, and perovskite), the ratios of which varied according to the cooling regime utilized. Microscopic observations indicated that the cooling regime also influenced the crystal size and morphology of the main phases, which consequently affected clinker reactivity. Furthermore, a smaller amount of substitute elements was incorporated in the main phases when cooling was slowed. Results showed that, in comparison to clinkers cooled at slower rates, air quenched clinkers reacted faster and exhibited a higher compressive strength at 7 days.
The potential use of steel slag from treated steel slag in belite-sulfoaluminate cements was investigated in this study. Cement clinkers with two phase compositions were synthesized, allowing the incorporation of different amounts of steel slag. The phase composition and microstructure of cement clinkers at three different sintering temperatures were studied by X-ray powder diffraction and the Rietveld method, as well as scanning electron microscopy with energy dispersive spectrometry. The results showed that the targeted phase composition of clinkers was achieved at a sintering temperature of 1250 °C. However, a higher amount of perovskite instead of ferrite was detected in the clinker with a higher content of Ti-bearing bauxite. Apart from the main phases, such as belite, calcium sulfoaluminate, and ferrite, several minor phases were identified, including mayenite, perovskite, periclase, and alkali sulfates. In both clinker mixtures, a higher content of MgO in the steel slags resulted in the formation of periclase. Furthermore, the hydration kinetics and compressive strength at 7 and 28 days were studied in two cements prepared from clinkers sintered at 1250 °C. As evidenced by the results of isothermal calorimetry, the hydration kinetics were also influenced by the minor clinker phases. Cement with a higher content of calcium sulfoaluminate phase developed a higher compressive strength.
The influence of temperature on the early hydration of belite-calcium sulfoaluminate cements with two different calcium sulfate to calcium sulfoaluminate molar ratios was investigated. The phase composition and phase assemblage development of cements prepared using molar ratios of 1 and 2.5 were studied at 25, 40 and 60 °C by in situ X-ray powder diffraction. The Rietveld refinement method was used for quantification. The degree of hydration after 24 h was highest at ambient temperatures, but early hydration was significantly accelerated at elevated temperatures. These differences were more noticeable when we increased the temperature from 25 °C to 40 °C, than it was increased from 40 °C to 60 °C. The amount of calcium sulfate added controls the amount of the precipitated ettringite, namely, the amount of ettringite increased in the cement with a higher molar ratio. The results showed that temperature also affects full width at half maximum of ettringite peaks, which indicates a decrease in crystallite size of ettringite at elevated temperatures due to faster precipitation of ettringite. When using a calcium sulfate to calcium sulfoaluminate molar ratio of 1, higher d-values of ettringite peaks were observed at elevated temperatures, suggesting that more ions were released from the cement clinker at elevated temperatures, allowing a higher ion uptake in the ettringite structure. At a molar ratio of 2.5, less clinker is available in the cement, therefore these differences were not observed.
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