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Chongchong Qi, Xinhang Xu, and Qiusong Chen, Hydration reactivity difference between dicalcium silicate and tricalcium silicate revealed from structural and Bader charge analysis, Int. J. Miner. Metall. Mater., 29(2022), No. 2, pp. 335-344. https://doi.org/10.1007/s12613-021-2364-5
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齐冲冲 E-mail: chongchong.qi@csu.edu.cn
水泥水化是水泥基材料强度产生的根本原因。通过阐明硅酸钙的结构特性和电子性质可以揭示其水化活性的差异。本文通过密度泛函理论对β-C2S和M3-C3S进行了综合比较，研究了它们在单胞、表面重构过程和单个水吸附后的原子结构以及Bader电荷。通过考虑成键特性和Bader电荷，确定了β-C2S和M3-C3S中不同类型的原子。在β-C2S中Ca和O原子分别被划分为两组和四组，M3-C3S中Si、Ca和O原子分别被分为三组、四组和四组。在M3-C3S的单胞中，作者注意到一种高活性的O原子具有特殊特征（即无O–Si键）,这可能是M3-C3S活性更高的根本原因。β-C2S和M3-C3S表面的价电子分布比其单胞分布的更加均匀，因此表明一些表面原子在弛豫后活性增强。在水的吸附过程中，β-C2S和M3-C3S的电子通过位置的改变和键的形成/断裂从表面转移到吸附的水分子上。Bader电荷分析表明：Ca/O原子的平均价电子数在β-C2S中为6.437/7.550，在M3-C3S中为6.481/7.537，M3-C3S中Ca和O原子的反应活性普遍高于β-C2S。此外，H2O在β-C2S和M3-C3S上的价电子的平均变化分别为0.041和0.226，H2O在M3-C3S表面获得的电子数比β-C2S更高。这项研究进一步解释了硅酸钙水化反应活性的差异，对高反应性和环境友好型水泥的设计大有裨益。
Cement hydration is the underlying mechanism for the strength development in cement-based materials. The structural and electronic properties of calcium silicates should be elucidated to reveal their difference in hydration reactivity. Here, we comprehensively compared β-C2S and M3-C3S and investigated their structural properties and Bader charge in the unit cell, during surface reconstruction and after single water adsorption via density functional theory. We identified different types of atoms in β-C2S and M3-C3S by considering the bonding characteristics and Bader charge. We then divided the atoms into the following groups: for β-C2S, Ca and O atoms divided into two and four groups, respectively; for M3-C3S, Ca, O, and Si atoms divided into four, four, and three groups, respectively. Results revealed that the valence electron distribution on the surface was more uniform than that on the unit cell, indicating that some atoms became more reactive after surface relaxation. During water adsorption, the electrons of β-C2S and M3-C3S were transferred from the surface to the adsorbed water molecules through position redistribution and bond formation/breaking. On this basis, we explained why β-C2S and M3-C3S had activity differences. A type of O atom with special bond characteristics (no O–Si bonds) and high reactivity existed in the unit cell of M3-C3S. Bader charge analysis showed that the reactivity of Ca and O atoms was generally higher in M3-C3S than in β-C2S. Ca/O atoms had average valence electron numbers of 6.437/7.550 in β-C2S and 6.481/7.537 in M3-C3S. Moreover, the number of electrons gained by water molecules in M3-C3S at the surface was higher than that in β-C2S. The average variations in the valence electrons of H2O on β-C2S and M3-C3S were 0.041 and 0.226, respectively. This study further explains the differences in the hydration reactivity of calcium silicates and would be also useful for the design of highly reactive and environmentally friendly cements.
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