Journal of the Chinese Ceramic Society, Volume. 53, Issue 5, 1225(2025)
Symbiotic Regulation and Carbonization Mechanism of γ-C2S and β-C2S in Low-calcium Clinker System
IntroductionCarbon emissions in the construction industry are increasing now. Against the backdrop of environmental factors and low-carbon economy, the research on reducing carbon emission in cement industry has garnered widespread attention. During the cement production procedure, the decomposition of carbonates during the calcination of raw materials is the main source of CO2 emissions. Therefore, reducing the calcium content in cement clinker is expexted to significantly reduce the carbon emissions, thereby achieving energy conservation and emission reduction in the industry. Unlike the C3S mineral in ordinary Portland cement clinker, CS, C3S2, and γ-C2S are three types of low calcium silicate minerals, but they are all non hydraulic minerals that cannot obtain a certain mechanical strength through traditional cement hydration. Former research revealed that the carbonation activity is higher than the hydration activity of above three low calcium minerals, and cement products can be prepared through carbonation curing.MethodsTo solve the problems of high energy consumption and high CO2 emissions in the production of ordinary Portland cement, low calcium silicate minerals (CS, C2S, and C3S2) with carbonation activity are used to replace C3S minerals. The strategy could not only reduce carbon emissions in cement production, but also enhance utilization of carbon. Research has found that incorporating β-C2S into the low calcium system of γ-C2S can significantly enhance the mechanical properties of the system. In most reported research work, the single minerals are often blended after firing, and then the carbonization properties of the mixed minerals are studied. How to burn the C2S minerals with the optimal crystal ratio in one step and to achieve the symbiosis of γ-C2S and β-C2S in the system remains a challenge. This work focuses on C2S minerals. By changing the calcination temperature, C2S minerals with different crystal ratios are treated in one step, and the relative content of γ-C2S and β-C2S in low calcium cement clinker is regulated. The symbiotic mechanism of the two and the influence of different mineral contents of β-C2S and γ-C2S on the carbonization performance of the material are studied. The carbonization products and mechanisms are explored, providing a theoretical basis for the application of low calcium fixed carbon cement in carbonization and new ideas for the carbonization research of C2S minerals. which has certain guiding significance for energy conservation and emission reduction in the cement industry.Results and discussionThis work used limestone and sandstone to obtain low calcium cement clinker with different proportions of γ-C2S and β-C2S by adjusting the calcination temperature. The carbonization and hardening mechanism of low calcium cement clinker was analyzed using thermogravimetric analysis, X-ray diffraction, pH value, conductivity and other testing methods. The results showed that the molar ratio of γ-C2S/β-C2S was between 0.19 and 2.63. As the ratio of γ-C2S/β-C2S decreased, the compressive strength of low calcium cement clinker after 24 hours of carbonization gradually increased. When the calcination temperature was 1340 ℃ and the ratio of γ-C2S/β-C2S was 0.19, the compressive strength of the system reached 163.32 MPa. The change in CO2 absorption of the sample is related to the carbonation activity of calcium silicate. The early carbonization reaction of the experimental group, mainly composed of γ-C2S minerals, is severe. There is a phenomenon of incomplete reaction in the test block. The experimental group mainly composed of β-C2S minerals has a longer duration of exothermic reaction, which is more conducive to the progress of carbonization reaction. Among them, the heat released by γ-C2S during the carbonization process promotes the easier dissolution of Ca2+ from β-C2S, facilitating the carbonization reaction of β-C2S. The addition of a small amount of γ-C2S (i.e. 8.13%) has a positive effect on the carbonization degree and strength of β-C2S. In addition, the dissolution of β-C2S leads to a gradual increase in the pH value of the suspension, changing the liquid phase environment and accelerating the dissolution rate of γ-C2S in water under alkaline conditions. The excellent compressive strength of the sample is attributed to its high degree of carbonization and dense microstructure. The higher the content of β-C2S minerals (γ-C2S/β-C2S ratio=0.19), the better crystallized calcite type calcium carbonate can be observed after carbonization, presenting a stacked and dense morphology. The samples mainly composed of γ-C2S minerals have weak particle bonding and loose structure after carbonization, showing amorphous calcium carbonate with many pores.ConclusionsTherefore, it can be concluded that the synergistic carbonization of γ-C2S and β-C2S mainly exists in two processes: the dissolution process before CO2 is introduced, and the carbonization reaction process after CO2 is introduced. Due to the action of water, β-C2S preferentially dissolves Ca2+, changing the liquid-phase environment around γ-C2S particles and promoting Ca2+ dissolution. After the introduction of CO2, the carbonization reaction of γ-C2S becomes more intense, releasing a large amount of heat that accelerates the dissolution of β-C2S minerals and promotes their carbonization reaction. The final carbonized product is mainly composed of stacked calcite, with a small amount of high polymer silica gel interspersed to bond the calcite. Therefore, the high content of β-C2S carbonized product shows a more tightly aggregation of particles and thus better performance.
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ZHANG Yunzi, WANG Yali, PEI Tianrui, ZHENG Yongchao, ZHAO Sixue. Symbiotic Regulation and Carbonization Mechanism of γ-C2S and β-C2S in Low-calcium Clinker System[J]. Journal of the Chinese Ceramic Society, 2025, 53(5): 1225
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Received: Oct. 30, 2024
Accepted: May. 29, 2025
Published Online: May. 29, 2025
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